Hydrazide compound and pesticidal use of the same

ABSTRACT

A hydrazide compound represented by the formula (1): 
     
       
         
         
             
             
         
       
     
     (wherein R 1 , R 2 , R 3 , R 4 , A 1 , A 2 , J, Q and n are defined in the specification) has excellent pesticidal activity.

This application is a Divisional of co-pending application Ser. No.11/992,490, filed on Mar. 24, 2008, which claims the priority ofJapanese Application Nos. 2005-299843 and 2006-144829, filed on Oct. 14,2010 and May 25, 2006 respectively, the entire contents of all arehereby incorporated by reference and for which priority is claimed under35 U.S.C. §120.

TECHNICAL FIELD

The present invention relates to a hydrazide compound and pesticidal useof the same.

BACKGROUND ART

In WO 01/70671, WO 03/015518, WO 03/016284, WO 03/016300 and WO03/024222, certain amide compounds are known to be compounds havingpesticidal activity.

DISCLOSURE OF THE INVENTION

The present invention is intended to provide a compound having excellentefficacy of controlling pests.

The present inventors have intensively studied in order to find out acompound having excellent efficacy of controlling pests and, as aresult, found out that a hydrazide compound represented by the followingformula (1) has excellent controlling efficacy. Thus, the presentinvention has been completed.

According to the present invention, there is provided:

(1) A hydrazide compound represented by the formula (1):

wherein

R¹ represents a hydrogen atom, a C1-C6 alkyl group optionallysubstituted with at least one halogen atom, a C2-C6 cyanoalkyl group, aC2-C6 alkoxyalkyl group optionally substituted with at least one halogenatom, a C2-C6 alkenyl group optionally substituted with at least onehalogen atom, a C3-C6 alkynyl group optionally substituted with at leastone halogen atom, or a C7-C9 phenyl alkyl group whose benzene ringmoiety may be substituted with 1 to 5 independent substituents selectedfrom the group consisting of (1) a halogen atom, (2) a cyano group, (3)a nitro group, (4) a C1-C6 alkyl group optionally substituted with atleast one halogen atom and (5) a C1-C6 alkoxy group optionallysubstituted with at least one halogen atom,

R² and R³ independently represent a hydrogen atom, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom, a C1-C6 acylgroup, a C2-C6 alkoxycarbonyl group, a C3-C7 N,N-dialkylcarbamoyl group,or a phenyl group optionally substituted with 1 to 5 independentsubstituents selected from the group consisting of (1) a halogen atom,(2) a cyano group, (3) a nitro group and (4) a C1-C6 alkyl groupoptionally substituted with at least one halogen atom,

R⁴ represents a halogen atom, a cyano group, a nitro group, a C1-C6alkyl group optionally substituted with at least one halogen atom, aC1-C6 alkoxy group optionally substituted with at least one halogenatom, a phenyl group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom, or two R⁴ groups which arebound to the adjacent carbon atoms are bound at their terminal ends toeach other to form a group T1 or T2

T1: —CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

T2: —(CR⁴⁵R⁴⁶)_(h)—(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ independently, represent a hydrogen atom,a halogen atom, a cyano group, a nitro group, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom, a C1-C6 alkoxygroup optionally substituted with at least one halogen atom, a C1-C6alkylthio group optionally substituted with at least one halogen atom, aC1-C6 alkylsulfinyl group optionally substituted with at least onehalogen atom, or a C1-C6 alkylsulfonyl group optionally substituted withat least one halogen atom,

R⁴⁵ and R⁴⁶ independently represent a hydrogen atom, or a C1-C6 alkylgroup optionally substituted with at least one halogen atom, and

h represents an integer of 3 or 4),

n represents an integer of 0 to 4 (provided that, when n is an integerof 2 or more, R⁴'s may be the same or different),

Q represents a group selected from Q1 to Q6:

Q1: —C(=A³¹)-R⁵ Q2: —C(=A³²)-OR⁶ Q3: —C(=A³³)-SR⁷ Q4: —C(=A³⁴)-NR⁸R⁹ Q5:—S(O)₂—R¹⁰ Q6: —S(O)₂—NR¹¹R¹²

(wherein A³¹, A³², A³³ and A³⁴ represent an oxygen atom or a sulfuratom,

R⁵ represents a hydrogen atom; a C2-C6 alkenyl group optionallysubstituted with at least one halogen atom; a C2-C6 alkynyl groupoptionally substituted with at least one halogen atom; a C1-C6 alkylgroup optionally substituted with one or more independent substituentsselected from the group consisting of (1) a halogen atom, (2) a C1-C6alkoxy group, (3) a C1-C6 alkylthio group, (4) a C1-C6 alkylsulfinylgroup, (5) a C1-C6 alkylsulfonyl group, (6) a C2-C6 dialkylamino groupand (7) a C3-C6 cycloalkyl group; a C3-C6 cycloalkyl group optionallysubstituted with one or more independent substituents selected from thegroup consisting of (1) a halogen atom, (2) a C1-C6 alkyl group; aphenyl group optionally substituted with 1 to 5 independent substituentsselected from the group consisting of (1) a halogen atom, (2) a cyanogroup, (3) a nitro group, (4) a C1-C6 alkyl group optionally substitutedwith at least one halogen atom, (5) a C1-C6 alkoxy group optionallysubstituted with at least one halogen atom, (6) a C1-C6 alkylthio groupoptionally substituted with at least one halogen atom, (7) a C1-C6alkylsulfinyl group optionally substituted with at least one halogenatom, (8) a C1-C6 alkylsulfonyl group optionally substituted with atleast one halogen atom, (9) a C2-C6 dialkylamino group optionallysubstituted with at least one halogen atom and (10) a C2-C6alkoxycarbonyl group optionally substituted with at least one halogenatom; a naphthyl group optionally substituted with 1 to 9 independentsubstituents selected from the group consisting of (1) a halogen atom,(2) a cyano group, (3) a nitro group, (4) a C1-C6 alkyl group optionallysubstituted with at least one halogen atom and (5) a C1-C6 alkoxy groupoptionally substituted with at least one halogen atom; a 5- to6-membered heteroaryl group optionally substituted with one or moreindependent substituents selected from the group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom and (5) aC1-C6 alkoxy group optionally substituted with at least one halogenatom; a 3- to 8-membered non-aromatic heterocyclic group optionallysubstituted with one or more independent substituents selected from thegroup consisting of (1) a halogen atom and (2) a C1-C6 alkyl group; aC7-C9 phenylalkyl group whose benzene ring moiety may be substitutedwith 1 to 5 independent substituents selected from the group consistingof (1) a halogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6alkyl group optionally substituted with at least one halogen atom and(5) a C1-C6 alkoxy group optionally substituted with at least onehalogen atom; or a C7-C9 phenoxyalkyl group whose benzene ring moietymay be substituted with 1 to 5 independent substituents selected fromthe group consisting of (1) a halogen atom, (2) a cyano group, (3) anitro group, (4) a C1-C6 alkyl group optionally substituted with atleast one halogen atom and (5) a C1-C6 alkoxy group optionallysubstituted with at least one halogen atom,

R⁶ and R⁷ represent a C1-C6 alkyl group optionally substituted with atleast one halogen atom; a C3-C6 alkoxyalkyl group optionally substitutedwith at least one halogen atom; a C2-C6 alkenyl group optionallysubstituted with at least one halogen atom; a C3-C6 alkynyl groupoptionally substituted with at least one halogen atom; a C3-C6cycloalkyl group optionally substituted with one or more independentsubstituents selected from the group consisting of (1) a halogen atomand (2) a C1-C6 alkyl group; a phenyl group optionally substituted with1 to 5 independent substituents selected from the group consisting of(1) a halogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6alkyl group optionally substituted with at least one halogen atom, (5) aC1-C6 alkoxy group optionally substituted with at least one halogenatom, (6) a C1-C6 alkylthio group optionally substituted with at leastone halogen atom, (7) a C1-C6 alkylsulfinyl group optionally substitutedwith at least one halogen atom, (8) a C1-C6 alkylsulfonyl groupoptionally substituted with at least one halogen atom, (9) a C2-C6dialkylamino group optionally substituted with at least one halogen atomand (10) a C2-C6 alkoxycarbonyl group optionally substituted with atleast one halogen atom; a 5- to 6-membered heteroaryl group optionallysubstituted with 1 to 5 independent substituents selected from the groupconsisting of (1) a halogen atom, (2) a cyano group, (3) a nitro group,(4) a C1-C6 alkyl group optionally substituted with at least one halogenatom and (5) a C1-C6 alkoxy group optionally substituted with at leastone halogen atom; or a C7-C9 phenylalkyl group whose benzene ring moietymay be substituted with 1 to 5 independent substituents selected fromthe group consisting of (1) a halogen atom, (2) a cyano group, (3) anitro group, (4) a C1-C6 alkyl group optionally substituted with atleast one halogen atom and (5) a C1-C6 alkoxy group optionallysubstituted with at least one halogen atom,

R⁸ and R⁹ independently represent a hydrogen atom; a C1-C6 alkyl groupoptionally substituted with at least one halogen atom; a C2-C6alkoxyalkyl group optionally substituted with at least one halogen atom;a C2-C6 alkenyl group optionally substituted with at least one halogenatom; a C3-C6 alkynyl group optionally substituted with at least onehalogen atom; a C3-C6 cycloalkyl group optionally substituted with oneor more independent substituents selected from the group consisting of(1) a halogen atom and (2) a C1-C6 alkyl group; a phenyl groupoptionally substituted with 1 to 5 independent substituents selectedfrom the group consisting of (1) a halogen atom, (2) a cyano group, (3)a nitro group, (4) a C1-C6 alkyl group optionally substituted with atleast one halogen atom, (5) a C1-C6 alkoxy group optionally substitutedwith at least one halogen atom, (6) a C1-C6 alkylthio group optionallysubstituted with at least one halogen atom, (7) a C1-C6 alkylsulfinylgroup optionally substituted with at least one halogen atom, (8) a C1-C6alkylsulfonyl group optionally substituted with at least one halogenatom, (9) a C2-C6 dialkylamino group optionally substituted with atleast one halogen atom and (10) a C2-C6 alkoxycarbonyl group optionallysubstituted with at least one halogen atom; a 5- to 6-memberedheteroaryl group optionally substituted with 1 to 5 independentsubstituents selected from the group consisting of (1) a halogen atom,(2) a cyano group, (3) a nitro group, (4) a C1-C6 alkyl group optionallysubstituted with at least one halogen atom and (5) a C1-C6 alkoxy groupoptionally substituted with at least one halogen atom; or a C7-C9phenylalkyl group whose benzene ring moiety may be substituted with 1 to5 independent substituents selected from the group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom and (5) aC1-C6 alkoxy group optionally substituted with at least one halogenatom; or R⁸ and R⁹ are taken together with the nitrogen atom to whichthey are bound to form a 3- to 8-membered non-aromatic heterocyclicgroup, the 3- to 8-membered non-aromatic heterocyclic group may contain,in the ring, one or more independent groups selected from the groupconsisting of (1) an oxygen atom, (2) a sulfur group and (3) a —NR^(a)—group (wherein R^(a) represents a C1-C6 alkyl group optionallysubstituted with at least one halogen atom, a C2-C6 alkoxycarbonyl groupoptionally substituted with at least one halogen atom, or a phenyl groupoptionally substituted with 1 to 5 independent substituents selectedfrom the group consisting of (1) a halogen atom, (2) a cyano group, (3)a nitro group, (4) a C1-C6 alkyl group optionally substituted with atleast one halogen atom and (5) a C1-C6 alkoxy group optionallysubstituted with at least one halogen atom), and carbon atom(s) in thering may be substituted with one or more independent substituentsselected from the group consisting of (1) a halogen atom, (2) a C1-C6alkyl group optionally substituted with at least one halogen atom and(3) a C2-C6 alkoxycarbonyl group optionally substituted with at leastone halogen atom,

R¹⁰ represents a C1-C6 alkyl group optionally substituted with at leastone halogen atom; a C3-C6 cycloalkyl group optionally substituted withone or more independent substituents selected from the group consistingof (1) a halogen atom and (2) a C1-C6 alkyl group optionally substitutedwith at least one halogen atom; or a phenyl group optionally substitutedwith 1 to 5 independent substituents selected from the group consistingof (1) a halogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6alkyl group optionally substituted with at least one halogen atom and(5) a C1-C6 alkoxy group optionally substituted with at least onehalogen atom, and

R¹¹ and R¹² independently represent a C1-C6 alkyl group optionallysubstituted with at least one halogen atom; a C3-C6 cycloalkyl groupoptionally substituted with one or more independent substituentsselected from the group consisting of (1) a halogen atom and (2) a C1-C6alkyl group optionally substituted with at least one halogen atom; or aphenyl group optionally substituted with 1 to 5 independent substituentsselected from the group consisting of (1) a halogen atom, (2) a cyanogroup, (3) a nitro group, (4) a C1-C6 alkyl group optionally substitutedwith at least one halogen atom and (5) a C1-C6 alkoxy group optionallysubstituted with at least one halogen atom; or R¹¹ and R¹² are takentogether with the nitrogen atom to which they are bound to form a 3- to8-membered non-aromatic heterocyclic group, the 3- to 8-memberednon-aromatic heterocyclic group may contain, in the ring, one or moreindependent groups selected from the group consisting of (1) an oxygenatom, (2) a sulfur atom and (3) a —NR^(b)-group (wherein R^(b)represents a C1-C6 alkyl group optionally substituted with at least onehalogen atom, a C2-C6 alkoxycarbonyl group optionally substituted withat least one halogen atom, or a phenyl group optionally substituted with1 to 5 independent substituents selected from the group consisting of(1) a halogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6alkyl group optionally substituted with at least one halogen atom and(5) a C1-C6 alkoxy group optionally substituted with at least onehalogen atom), and carbon atom(s) in the ring may be substituted withone or more independent substituents selected from the group consistingof (1) a halogen atom, (2) a C1-C6 alkyl group optionally substitutedwith at least one halogen atom and (3) a C2-C6 alkoxycarbonyl groupoptionally substituted with at least one halogen atom),

J represents a group represented by J1 or J2:

(wherein X^(a), Y^(a), Z^(a), X^(b), Y^(b) and Z^(b) independentlyrepresent CH or a nitrogen atom,

R^(13a) and R^(13b) represent a C1-C6 alkyl group optionally substitutedwith at least one halogen atom; a C2-C6 cyanoalkyl group; a C2-C6alkoxyalkyl group optionally substituted with at least one halogen atom;a C2-C6 alkenyl group optionally substituted with at least one halogenatom; a C2-C6 alkynyl group optionally substituted with at least onehalogen atom; a C3-C6 cycloalkyl group optionally substituted with oneor more independent substituents selected from the group consisting of(1) a halogen atom and (2) a C1-C6 alkyl group; a phenyl groupoptionally substituted with 1 to 5 independent substituents selectedfrom the group consisting of (1) a halogen atom, (2) a cyano group, (3)a nitro group, (4) a C1-C6 alkyl group optionally substituted with atleast one halogen atom, (5) a C1-C6 alkoxy group optionally substitutedwith at least one halogen atom, (6) a C1-C6 alkylthio group optionallysubstituted with at least one halogen atom, (7) a C1-C6 alkylsulfinylgroup optionally substituted with at least one halogen atom and (8) aC1-C6 alkylsulfonyl group optionally substituted with at least onehalogen atom; a 5- to 6-membered heteroaryl group optionally substitutedwith one or more independent substituents selected from the groupconsisting of (1) a halogen atom, (2) a cyano group, (3) a nitro group,(4) a C1-C6 alkyl group optionally substituted with at least one halogenatom and (5) a C1-C6 alkoxy group optionally substituted with at leastone halogen atom; a C7-C9 phenylalkyl group whose benzene ring moietymay be substituted with one or more independent substituents selectedfrom the group consisting of (1) a halogen atom, (2) a cyano group, (3)a nitro group, (4) a C1-C6 alkyl group optionally substituted with atleast one halogen atom and (5) a C1-C6 alkoxy group optionallysubstituted with at least one halogen atom; or a C7-C9 pyridinylalkylgroup whose pyridine ring moiety may be substituted with one or moreindependent substituents selected from the group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom and (5) aC1-C6 alkoxy group optionally substituted with at least one halogenatom,

R^(14a) and R^(14b) represent a halogen atom; a cyano group; a nitrogroup; a C1-C6 alkyl group optionally substituted with at least onehalogen atom; a C1-C6 alkoxy group optionally substituted with at leastone halogen atom; a C2-C6 cyanoalkyloxy group; a C3-C6 alkoxyalkyloxygroup optionally substituted with at least one halogen atom; a C3-C6alkenyloxy group optionally substituted with at least one halogen atom;a C3-C6 alkynyloxy group optionally substituted with at least onehalogen atom; a C1-C6 alkylthio group optionally substituted with atleast one halogen atom; a C1-C6 alkylsulfinyl group optionallysubstituted with at least one halogen atom; a C1-C6 alkylsulfonyl groupoptionally substituted with at least one halogen atom; a phenyl groupoptionally substituted with 1 to 5 independent substituents selectedfrom the group consisting of (1) a halogen atom, (2) a cyano group, (3)a nitro group, (4) a C1-C6 alkyl group optionally substituted with atleast one halogen atom and (5) a C1-C6 alkoxy group optionallysubstituted with at least one halogen atom; a 5- to 6-memberedheteroaryl group optionally substituted with one or more independentsubstituents selected from the group consisting of (1) a halogen atom,(2) a cyano group, (3) a nitro group, (4) a C1-C6 alkyl group optionallysubstituted with at least one halogen atom and (5) a C1-C6 alkoxy groupoptionally substituted with at least one halogen atom; or a phenoxygroup optionally substituted with 1 to 5 independent substituentsselected from the group consisting of (1) a halogen atom, (2) a cyanogroup, (3) a nitro group, (4) a C1-C6 alkyl group optionally substitutedwith at least one halogen atom and (5) a C1-C6 alkoxy group optionallysubstituted with at least one halogen atom,

p represents an integer of 0 to 3, and

q represents an integer of 0 to 3 (provided that, when p is an integerof 2 or 3, two or more R¹⁴'s may be the same or different and, when q isan integer of 2 or 3, two or more R^(14b)'s may be the same ordifferent), and

A¹ and A² independently represent an oxygen atom or a sulfur atom(hereinafter referred to as the present compound)

(2) The compound according to the above (1), wherein n is an integer of0 to 3.

(3) The compound according to the above (2), wherein R⁴ is a halogenatom, a cyano group, a C1-C6 alkyl group optionally substituted with atleast one halogen atom, a C1-C6 alkoxy group optionally substituted withat least one halogen atom, a phenyl group optionally substituted with atleast one halogen atom, or two R⁴ groups which are bound to the adjacentcarbon atoms are bound at their terminal ends to form a group T1:

—CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ represent a hydrogen atom).

(4) The compound according to the above (3), wherein R⁴ is a fluorineatom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, amethyl group, an ethyl group, a trifluoromethyl group, a methoxy group,a phenyl group, or two R⁴ groups which are bound to the adjacent carbonatoms are bound at their terminal ends to form a group T1:—CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ represent a hydrogen atom).

(5) The compound according to any one of the above (1) to (4), wherein

J is J1,

Y^(a) is CH,

R^(13a) is a C1-C6 alkyl group optionally substituted with at least onehalogen atom; a C3-C6 cycloalkyl group optionally substituted with oneor more independent substituents selected from the group consisting of(1) a halogen atom and (2) a C1-C6 alkyl group; a phenyl groupoptionally substituted with 1 to 5 independent substituents selectedfrom the group consisting of (1) a halogen atom, (2) a cyano group, (3)a nitro group, (4) a C1-C6 alkyl group optionally substituted with atleast one halogen atom, (5) a C1-C6 alkoxy group optionally substitutedwith at least one halogen atom, (6) a C1-C6 alkylthio group optionallysubstituted with at least one halogen atom, (7) a C1-C6 alkylsulfinylgroup optionally substituted with at least one halogen atom and (8) aC1-C6 alkylsulfonyl group optionally substituted with at least onehalogen atom; or a 5- to 6-membered heteroaryl group optionallysubstituted with one or more independent substituents selected from thegroup consisting of (1) a halogen atom, (2) a cyano group, (3) a nitrogroup, (4) a C1-C6 alkyl group optionally substituted with at least onehalogen atom and (5) a C1-C6 alkoxy group optionally substituted with atleast one halogen atom,

R^(14a) is a halogen atom; a cyano group; a C1-C6 alkyl group optionallysubstituted with at least one halogen atom; a C1-C6 alkylthio groupoptionally substituted with at least one halogen atom; a C1-C6alkylsulfinyl group optionally substituted with at least one halogenatom; a C1-C6 alkylsulfonyl group optionally substituted with at leastone halogen atom; or a phenyl group optionally substituted with 1 to 5independent substituents selected from the group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom and (5) aC1-C6 alkoxy group optionally substituted with at least one halogenatom, and

p is an integer of 0 to 2.

(6) The compound according to any one of the above (1) to (4), wherein

J is J2, Y^(b) is CH,

R^(13b) is a C1-C6 alkyl group optionally substituted with at least onehalogen atom,

R^(14b) is a C1-C6 alkyl group optionally substituted with at least onehalogen atom, or a phenyl group optionally substituted with 1 to 5independent substituents selected from the group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom and (5) aC1-C6 alkoxy group optionally substituted with at least one halogenatom, and

q is 1.

(7) The compound according to any one of the above (1) to (6), whereinA¹ and A² are an oxygen atom, and R¹ is a hydrogen atom or a methylgroup.

(8) The compound according to any one of the above (1) to (7), wherein

Q is Q¹,

A³¹ is an oxygen atom, and

R⁵ is a hydrogen atom; a C1-C6 alkyl group optionally substituted withone or more independent substituents selected from the group consistingof (1) a halogen atom, (2) a C1-C6 alkoxy group, (3) a C1-C6 alkylthiogroup, (4) a C1-C6 alkylsulfinyl group, (5) a C1-C6 alkylsulfonyl group,(6) a C2-C6 dialkylamino group and (7) a C3-C6 cycloalkyl group; a C3-C6cycloalkyl group optionally substituted with one or more independentsubstituents selected from the group consisting of (1) a halogen and (2)a C1-C6 alkyl group; a phenyl group optionally substituted with 1 to 5independent substituents selected from the group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom, (5) a C1-C6alkoxy group optionally substituted with at least one halogen atom, (6)a C1-C6 alkylthio group optionally substituted with at least one halogenatom, (7) a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, (8) a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom, (9) a C2-C6 dialkylaminogroup optionally substituted with at least one halogen atom and (10) aC2-C6 alkoxycarbonyl group optionally substituted with at least onehalogen atom; a 5- to 6-membered heteroaryl group optionally substitutedwith one or more independent substituents selected from the groupconsisting of (1) a halogen atom, (2) a cyano group, (3) a nitro group,(4) a C1-C6 alkyl group optionally substituted with at least one halogenatom and (5) a C1-C6 alkoxy group optionally substituted with at leastone halogen atom; or a 3 to 8-membered non-aromatic heterocyclic groupoptionally substituted with one or more independent groups selected fromthe group consisting of (1) a halogen atom and (2) a C1-C6 alkyl group.

(9) The compound according to the above (8), wherein R⁵ is a hydrogenatom, a methyl group, an ethyl group, a tert-butyl group, a cyclopropylgroup, a phenyl group, a 3-methylphenyl group, a 4-methoxyphenyl group,a 2-pyridinyl group, or a morpholino group.

(10) The compound according to any one of the above (1) to (7), wherein

Q is Q2,

A³² is an oxygen atom, and

R⁶ is a C1-C6 alkyl group optionally substituted with at least onehalogen atom; a C2-C6 alkenyl group optionally substituted with at leastone halogen atom; or a phenyl group optionally substituted with 1 to 5independent substituents selected from the group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom, (5) a C1-C6alkoxy group optionally substituted with at least one halogen atom, (6)a C1-C6 alkylthio group optionally substituted with at least one halogenatom, (7) a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, (8) a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom, (9) a C2-C6 dialkylaminogroup optionally substituted with at least one halogen atom and (10) aC2-C6 alkoxy carbonyl group optionally substituted with at least onehalogen atom.

(11) The compound according to the above (10), wherein R⁶ is a methylgroup, an ethyl group, a propyl group, an isopropyl group, a butylgroup, a sec-butyl group, a 2-propenyl group, or a phenyl group.

(12) The compound according to any one of the above (1) to (7), wherein

Q is Q4,

A³⁴ is an oxygen atom, and

R⁸ and R⁹ independently represent a hydrogen atom; a C1-C6 alkyl groupoptionally substituted with at least one halogen atom; or a phenyl groupoptionally substituted with 1 to 5 independent substituents selectedfrom the group consisting of (1) a halogen atom, (2) a cyano group, (3)a nitro group, (4) a C1-C6 alkyl group optionally substituted with atleast one halogen atom, (5) a C1-C6 alkoxy group optionally substitutedwith at least one halogen atom, (6) a C1-C6 alkylthio group optionallysubstituted with at least one halogen atom, (7) a C1-C6 alkylsulfinylgroup optionally substituted with at least one halogen atom, (8) a C1-C6alkylsulfonyl group optionally substituted with at least one halogenatom, (9) a C2-C6 dialkylamino group optionally substituted with atleast one halogen atom and (10) a C2-C6 alkoxy carbonyl group optionallysubstituted with at least one halogen atom.

(13) The compound according to the above (12), wherein R⁸ and R⁹, each,independently, represent a hydrogen atom, a methyl group, an ethylgroup, or a phenyl group.

(14) The compound according to any one of the above (1) to (13), whereinR² is a hydrogen atom or a methyl group, and R³ is a hydrogen atom, amethyl group, an isopropyl group, or a methoxycarbonyl group.

(15) The compound according to the above (1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R⁴ is a halogen atom, a cyano group, a C1-C6 alkyl group optionallysubstituted with at least one halogen atom, a C1-C6 alkoxy groupoptionally substituted with at least one halogen atom, or a phenyl groupoptionally substituted with at least one halogen atom, or two R⁴ groupswhich are bound to the adjacent carbon atoms are bound at their terminalends to form

T1: —CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ represent a hydrogen atom),

n is an integer of 0 to 3,

Q is a group represented by Q1 to Q6:

Q1: —C(=A³¹)-R⁵ Q2: —C(=A³²)-OR⁶ Q3: —C(=A³³)-SR⁷ Q4: —C(=A³⁴)-NR⁸R⁹ Q5:—S(O)₂—R¹⁰ Q6: —S(O)₂—NR¹¹R¹²

(wherein A³¹, A³² and A³³ are an oxygen atom, A³⁴ is an oxygen atom or asulfur atom,

R⁵ is a hydrogen atom; a C1-C6 alkyl group optionally substituted withone or more independent substituents selected from the group consistingof (1) a halogen atom, (2) a C1-C6 alkoxy group, (3) a C1-C6 alkylthiogroup, (4) a C1-C6 alkylsulfinyl group, (5) a C1-C6 alkylsulfonyl group,(6) a C2-C6 dialkylamino group and (7) a C3-C6 cycloalkyl group; a C3-C6cycloalkyl group optionally substituted with one or more independentsubstituents selected from the group consisting of (1) a halogen atomand (2) a C1-C6 alkyl group; a phenyl group optionally substituted with1 to 5 independent substituents selected from the group consisting of(1) a halogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6alkyl group optionally substituted with at least one halogen atom, (5) aC1-C6 alkoxy group optionally substituted with at least one halogenatom, (6) a C1-C6 alkylthio group optionally substituted with at leastone halogen atom, (7) a C1-C6 alkylsulfinyl group optionally substitutedwith at least one halogen atom, (8) a C1-C6 alkylsulfonyl groupoptionally substituted with at least one halogen atom, (9) a C2-C6dialkylamino group optionally substituted with at least one halogen atomand (10) a C2-C6 alkoxycarbonyl group optionally substituted with atleast one halogen atom; a 5- to 6-membered heteroaryl group optionallysubstituted with one or more independent substituents selected from thegroup consisting of (1) a halogen atom, (2) a cyano group, (3) a nitrogroup, (4) a C1-C6 alkyl group optionally substituted with at least onehalogen atom and (5) a C1-C6 alkoxy group optionally substituted with atleast one halogen atom; or a 3- to 8-membered non-aromatic heterocyclicgroup optionally substituted with one or more independent substituentsselected from the group consisting of (1) a halogen atom and (2) a C1-C6alkyl group,

R⁶ is a C1-C6 alkyl group optionally substituted with at least onehalogen atom; a C2-C6 alkenyl group optionally substituted with at leastone halogen atom; or a phenyl group optionally substituted with 1 to 5independent substituents selected from the group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom, (5) a C1-C6alkoxy group optionally substituted with at least one halogen atom, (6)a C1-C6 alkylthio group optionally substituted with at least one halogenatom, (7) a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, (8) a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom, (9) a C2-C6 dialkylaminogroup optionally substituted with at least one halogen atom and (10) aC2-C6 alkoxycarbonyl group optionally substituted with at least onehalogen atom,

R⁷ is a C1-C6 alkyl group optionally substituted with at least onehalogen atom,

R⁸ and R⁹ independently represent a hydrogen atom; a C1-C6 alkyl groupoptionally substituted with at least one halogen atom; or a phenyl groupoptionally substituted with 1 to 5 independent substituents selectedfrom the group consisting of (1) a halogen atom, (2) a cyano group, (3)a nitro group, (4) a C1-C6 alkyl group optionally substituted with atleast one halogen atom, (5) a C1-C6 alkoxy group optionally substitutedwith at least one halogen atom, (6) a C1-C6 alkylthio group optionallysubstituted with at least one halogen atom, (7) a C1-C6 alkylsulfinylgroup optionally substituted with at least one halogen atom, (8) a C1-C6alkylsulfonyl group optionally substituted with at least one halogenatom, (9) a C2-C6 dialkylamino group optionally substituted with atleast one halogen atom and (10) a C2-C6 alkoxycarbonyl group optionallysubstituted with at least one halogen atom,

R¹⁰ is a C1-C6 alkyl group optionally substituted with at least onehalogen atom, and

R¹¹ and R¹² independently represent a C1-C6 alkyl group optionallysubstituted with at least one halogen atom),

J is a group represented by J1 or J2:

(wherein X^(a) is CH or a nitrogen atom, Y^(a) is CH, Z^(a) is CH or anitrogen atom, X^(b) is CH or a nitrogen atom, Y^(b) is CH, and Z^(b) isCH or a nitrogen atom,

R^(13a) is a C1-C6 alkyl group optionally substituted with at least onehalogen atom; a C3-C6 cycloalkyl group optionally substituted with oneor more independent substituents selected from the group consisting of(1) a halogen atom and (2) a C1-C6 alkyl group; a phenyl groupoptionally substituted with 1 to 5 independent substituents selectedfrom the group consisting of (1) a halogen atom, (2) a cyano group, (3)a nitro group, (4) a C1-C6 alkyl group optionally substituted with atleast one halogen atom, (5) a C1-C6 alkoxy group optionally substitutedwith at least one halogen atom, (6) a C1-C6 alkylthio group optionallysubstituted with at least one halogen atom, (7) a C1-C6 alkylsulfinylgroup optionally substituted with at least one halogen atom and (8) aC1-C6 alkylsulfonyl group optionally substituted with at least onehalogen atom; or a 5- to 6-membered heteroaryl group optionallysubstituted with one or more independent substituents selected from thegroup consisting of (1) a halogen atom, (2) a cyano group, (3) a nitrogroup, (4) a C1-C6 alkyl group optionally substituted with at least onehalogen atom and (5) a C1-C6 alkoxy group optionally substituted with atleast one halogen atom,

R^(13b) is a C1-C6 alkyl group-optionally substituted with at least onehalogen atom,

R^(14a) is a halogen atom; a cyano group; a C1-C6 alkyl group optionallysubstituted with at least one halogen atom; a C1-C6 alkylthio groupoptionally substituted with at least one halogen atom; a C1-C6alkylsulfinyl group optionally substituted with at least one halogenatom; a C1-C6 alkylsulfonyl group optionally substituted with at leastone halogen atom; or a phenyl group optionally substituted with 1 to 5independent substituents selected from the group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom and (5) aC1-C6 alkoxy group optionally substituted with at least one halogenatom,

R^(14b) is a C1-C6 alkyl group optionally substituted with at least onehalogen atom; or a phenyl group optionally substituted with 1 to 5independent substituents selected from the group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom and (5) aC1-C6 alkoxy group optionally substituted with at least one halogenatom,

p is an integer of 0 to 2,

q is 1,

(provided that, when p is 2, two R^(14a)'s may be the same ordifferent)), and

A¹ and A² are an oxygen atom.

(16) A hydrazide compound represented by the formula (1-1):

wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a C1-C6 alkyl group optionally substituted with at least onehalogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a hydrogen atom, a halogen atom, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom, a C1-C6 alkoxygroup optionally substituted with at least one halogen atom, or a phenylgroup optionally substituted with at least one halogen atom,

R^(4b), R^(4c) and R^(4d) are independently a hydrogen atom, a halogenatom, a cyano group, a C1-C6 alkyl group optionally substituted with atleast one halogen atom, or

R^(4b) and R^(4c) are bound to each other at their terminal ends to forma group: —CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ represent a hydrogen atom),

M is OR⁶, SR⁷ or NR⁸R⁹

(wherein R⁶ and R⁷ are a C1-C6 alkyl group optionally substituted withat least one halogen atom, a C3-C6 alkoxyalkyl group optionallysubstituted with at least one halogen atom, a C2-C6 alkenyl groupoptionally substituted with at least one halogen atom, or a C3-C6alkynyl group optionally substituted with at least one halogen atom,

R⁸ and R⁹ are independently a hydrogen atom, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom, a C2-C6 alkenylgroup optionally substituted with at least one halogen atom, a C3-C6alkynyl group optionally substituted with at least one halogen atom, or

R⁸ and R⁹ are taken together with the nitrogen atom to which they arebound to form a pyrrolidin-1-yl group, a piperidino group, ahexamethyleneimin-1-yl group, a heptamethyleneimin-1-yl group, amorpholino group, a thiomorpholin-4-yl group, or a4-phenylpiperazin-1-yl group),

X^(a) is a nitrogen atom or CR^(14ax)

(wherein R^(14ax) represents a hydrogen atom, a halogen atom, a cyanogroup, a C1-C6 alkyl group optionally substituted with at least onehalogen atom, a C1-C6 alkylthio group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfinyl group optionallysubstituted with at least one halogen atom),

R^(14ay) is a hydrogen atom, a halogen atom, a cyano group, a C1-C6alkyl group optionally substituted with at least one halogen atom, aC1-C6 alkylthio group optionally substituted with at least one halogenatom, a C1-C6 alkylsulfinyl group optionally substituted with at leastone halogen atom, a C1-C6 alkylsulfonyl group optionally substitutedwith at least one halogen atom, or a phenyl group,

R^(14az) is a hydrogen atom,

X¹⁸ is a nitrogen atom or CR^(18e)

(wherein R^(18e) is a hydrogen atom or a halogen atom), and

R^(18a), R^(18b), R^(18c) and R^(18d) are independently a hydrogen atomor a halogen atom.

(17) A hydrazide compound represented by the formula (1-1):

wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a hydrogen atom, a halogen atom, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom, a C1-C6 alkoxygroup optionally substituted with at least one halogen atom, or a phenylgroup optionally substituted with at least one halogen atom,

R^(4b), R^(4c) and R^(4d) are independently a hydrogen atom, a halogenatom, a cyano group, a C1-C6 alkyl group optionally substituted with atleast one halogen atom, or

R^(4b) and R^(4c) are bound to each other at their terminal ends to forma group: —CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ represent a hydrogen atom),

M is a hydrogen atom,

X^(a) is a nitrogen atom or CR^(14ax)

(wherein R^(14ax) is a hydrogen atom, a halogen atom, a cyano group, aC1-C6 alkyl group optionally substituted with at least one halogen atom,a C1-C6 alkoxy group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom),

R^(14ay) is a hydrogen atom, a halogen atom, a cyano group, a C1-C6alkyl group optionally substituted with at least one halogen atom, aC1-C6 alkylthio group optionally substituted with at least one halogenatom, a C1-C6 alkylsulfinyl group optionally substituted with at leastone halogen atom, a C1-C6 alkylsulfonyl group optionally substitutedwith at least one halogen atom, or a phenyl group,

R^(14az) is a hydrogen atom,

X¹⁸ is a nitrogen atom or CR^(18e)

(wherein R^(18e) is a hydrogen atom or a halogen atom), and

R^(18a), R^(18b), R^(18c) and R^(18d) are independently a hydrogen atomor a halogen atom.

(18) A hydrazide compound represented by the formula (II):

wherein

R^(1-i) represents a hydrogen atom, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom,

R^(2-i) represents a hydrogen atom or a methyl group,

R^(4a) represents a halogen atom, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom,

R^(4b), R^(4c) and R^(4d) independently, represent a hydrogen atom, ahalogen atom, a cyano group, a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

or R^(4b) and R^(4c) are bound at an end to form a group T1:

—CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴, each, independently, represent ahydrogen atom, a halogen atom, a cyano group, or a C1-C6 alkyl groupoptionally substituted with at least one halogen atom),

X^(a) represents a nitrogen atom or CR^(14ax)

(wherein R^(14ax) represents a hydrogen atom, a halogen atom, a cyanogroup, a C1-C6 alkyl group optionally substituted with at least onehalogen atom, a C1-C6 alkoxy group optionally substituted with at leastone halogen atom, a C1-C6 alkylthio group optionally substituted with atleast one halogen atom, a C1-C6 alkylsulfinyl group optionallysubstituted with at least one halogen atom, or a C1-C6 alkylsulfonylgroup optionally substituted with at least one halogen atom),

R^(14ay) and R^(14az) independently represent a hydrogen atom, a halogenatom, a cyano group, a C1-C6 alkyl group optionally substituted with atleast one halogen atom, a C1-C6 alkoxy group optionally substituted withat least one halogen atom, a C1-C6 alkylthio group optionallysubstituted with at least one halogen atom, a C1-C6 alkylsulfinyl groupoptionally substituted with at least one halogen atom, or a C1-C6alkylsulfonyl group optionally substituted with at least one halogenatom,

X¹⁸ represents a nitrogen atom or CR^(18e),

(wherein R^(18e) represents a hydrogen atom, a halogen atom, or a C1-C6alkyl group optionally substituted with at least one halogen atom)

R^(18a) represents a halogen atom, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom, and

R^(18b), R^(18c) and R^(18d) independently represent a hydrogen atom, ahalogen atom, or a C1-C6 alkyl group optionally substituted with atleast one halogen atom.

(19) The compound according to the above (18), wherein R^(2-i) is amethyl group.

(20) A pesticide comprising the compound according to any one of theabove (1) to (17) as an active ingredient.

(21) A method of controlling a pest which comprises applying thecompound according to any one of the above (1) to (17) directly to apest or to a place where a pest inhabits.

(22) Use of the compound according to any one of the above (1) to (17)for controlling a pest.

(23) Use of the compound according to any one of the above (1) to (17)for manufacturing a pesticidal preparation.

Hereinafter, preferred embodiments of the present invention will beillustrated.

R^(14a) used herein represents a group which can substitute for ahydrogen atom of a ring constituting CH of a group represented by J1,and R^(14b) represents a group which can substitute for a hydrogen atomof a ring constituting CH of a group represented by J2.

In the present invention, examples of a halogen atom include a fluorineatom, a chlorine atom, a bromine atom and an iodine atom.

In R¹, R² and R³, examples of the “C1-C6 alkyl group optionallysubstituted with at least one halogen atom” include a methyl group, anethyl group, a 2,2,2-trifluoroethyl group, a propyl group, an isopropylgroup, a butyl group, an isobutyl group, a sec-butyl group, a tert-butylgroup, a pentyl group and a hexyl group.

In R¹, examples of the “C2-C6 cyanoalkyl group” include a cyanomethylgroup and a 2-cyanoethyl group;

examples of the “C2-C6 alkoxyalkyl group optionally substituted with atleast one halogen atom” include a 2-methoxyethyl group, a 2-ethoxyethylgroup and a 2-isopropyloxyethyl group;

examples of the “C2-C6 alkenyl group optionally substituted with atleast one halogen atom” include a 2-propenyl group, a3-chloro-2-propenyl group, a 2-chloro-2-propenyl group, a3,3-dichloro-2-propenyl group, a 2-butenyl group, a 3-butenyl group, a2-methyl-2-propenyl group, a 3-methyl-2-butenyl group, a 2-pentenylgroup and a 2-hexenyl group;

example of the “C3-C6 alkynyl group optionally substituted with at leastone halogen atom” include a 2-propynyl group, a 3-chloro-2-propynylgroup, a 3-bromo-2-propynyl group, a 2-butynyl group and a 3-butynylgroup; and

examples of the “C7-C9 phenylalkyl group whose benzene ring moiety maybe substituted with 1 to 5 independent groups selected from the groupconsisting of (1) a halogen atom, (2) a cyano group, (3) a nitro group,(4) a C1-C6 alkyl group optionally substituted with at least one halogenatom and (5) a C1-C6 alkoxy group optionally substituted with at leastone halogen atom” include a benzyl group, a 1-phenylethyl group, a2-phenylethyl group, a 2-chlorobenzyl group, a 3-chlorobenzyl group, a4-chlorobenzyl group, a 2-cyanobenzyl group, a 3-cyanobenzyl group, a4-cyanobenzyl group, a 2-nitrobenzyl group, a 3-nitrobenzyl group, a4-nitrobenzyl group, a 2-methylbenzyl group, a 3-methylbenzyl group, a4-methylbenzyl group, a 2-(trifluoromethyl)benzyl group, a3-(trifluoromethyl)benzyl group, a 4-(trifluoromethyl)benzyl group, a2-methoxybenzyl group, a 3-methoxybenzyl group and a 4-methoxybenzylgroup.

In R² and R³, examples of the “C1-C6 acyl group” include a formyl group,an acetyl group, a propionyl group, an isobutyryl group and atrimethylacetyl group;

examples of the “C2-C6 alkoxycarbonyl group” include a methoxycarbonylgroup, an ethoxycarbonyl group, an isopropoxycarbonyl group and atert-butoxycarbonyl group;

examples of the “C3-C7 N,N-dialkylcarbamoyl group” include aN,N-dimethylcarbamoyl group and a N,N-diethylcarbamoyl group; and

examples of the “phenyl group optionally substituted with 1 to 5independent groups selected from the group consisting of (1) a halogenatom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkyl groupoptionally substituted with at least one halogen atom and (5) a C1-C6alkyl group optionally substituted with at least one halogen atom”include a phenyl group, a 2-chlorophenyl group, a 3-chlorophenyl group,a 4-chlorophenyl group, a 2-cyanophenyl group, a 3-cyanophenyl group, a4-cyanophenyl group, a 2-nitrophenyl group, a 3-nitrophenyl group, a4-nitrophenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a4-methylphenyl group, a 2-(trifluoromethyl)phenyl group, a3-(trifluoromethyl)phenyl group and a 4-(trifluoromethyl)phenyl group.

In R⁴, R⁴¹, R⁴², R⁴³ and R⁴⁴, examples of the “C1-C6 alkyl groupoptionally substituted with at least one halogen atom” include a methylgroup, a trifluoromethyl group, an ethyl group, a propyl group, anisopropyl group, a butyl group, an isobutyl group, a sec-butyl group, atert-butyl group, a pentyl group and a hexyl group.

In R⁴, R⁴¹, R⁴², R⁴³ and R⁴⁴, examples of the “C1-C6 alkoxy groupoptionally substituted with at least one halogen atom” include a methoxygroup, a trifluoromethoxy group, an ethoxy group, a2,2,2-trifluoroethoxy group, a propyloxy group, an isopropyloxy group, abutoxy group, an isobutyloxy group, a sec-butoxy group, a tert-butoxygroup, a pentyloxy group and a hexyloxy group.

In R⁴, R⁴¹, R⁴², R⁴³ and R⁴⁴, examples of the “C1-C6 alkylthio groupoptionally substituted with at least one halogen atom” include amethylthio group, a trifluoromethylthio group and an ethylthio group.

In R⁴, R⁴¹, R⁴², R⁴³ and R⁴⁴, examples of the “C1-C6 alkylsulfinyl groupoptionally substituted with at least one halogen atom” include amethylsulfinyl group, a trifluoromethylsulfinyl group and anethylsulfinyl group.

In R⁴, R⁴¹, R⁴², R⁴³ and R⁴⁴, examples of the “C1-C6 alkylsulfonyl groupoptionally substituted with at least one halogen atom” include amethylsulfonyl group, a trifluoromethylsulfonyl group and anethylsulfonyl group.

In R⁴, examples of the “phenyl group optionally substituted with atleast one halogen atom” include a phenyl group, a 2-chlorophenyl group,a 3-chlorophenyl group and a 4-chlorophenyl group.

In R⁴⁵ and R⁴⁶, examples of the “C1-C6 alkyl group optionallysubstituted with at least one halogen atom” include a methyl group, atrifluoromethyl group, and an ethyl group.

In R⁵, examples of the “C2-C6 alkenyl group optionally substituted withat least one halogen atom” include a vinyl group, a 1-propenyl group, a2-propenyl group, a 1-methylvinyl group, a 2-chlorovinyl group and a2-methyl-1-propenyl group;

examples of the “C2-C6 alkynyl group optionally substituted with atleast one halogen atom” include an ethynyl group;

examples of the “C1-C6 alkyl group optionally substituted with one ormore independent substituents selected from the group consisting of (1)a halogen atom, (2) a C1-C6 alkoxy group, (3) a C1-C6 alkylthio group,(4) a C1-C6 alkylsulfinyl group, (5) a C1-C6 alkylsulfonyl group, (6) aC2-C6 dialkylamino group and (7) a C3-C6 cycloalkyl group” include amethyl group, a trifluoromethyl group, a trichloromethyl group, achloromethyl group, a dichloromethyl group, a fluoromethyl group, adifluoromethyl group, a methoxymethyl group, an ethoxymethyl group, amethylthiomethyl group, an ethylthiomethyl group, a methylsulfinylmethylgroup, a methylsulfonylmethyl group, a dimethylaminomethyl group, acyclopropylmethyl group, a cyclopentylmethyl group, a cyclohexylmethylgroup, an ethyl group, a pentafluoroethyl group, a propyl group, anisopropyl group, a butyl group, an isobutyl group, a sec-butyl group, atert-butyl group, a pentyl group and a hexyl group;

examples of the “C3-C6 cycloalkyl group optionally substituted with oneor more independent substituents selected from the group consisting of(1) a halogen atom and (2) a C1-C6 alkyl group” include a cyclopropylgroup, a 2-methylcyclopropyl group, a cyclobutyl group, a cyclopentylgroup and a cyclohexyl group;

examples of the “phenyl group optionally substituted with 1 to 5independent substituents selected from the group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom, (5) a C1-C6alkoxy group optionally substituted with at least one halogen atom, (6)a C1-C6 alkylthio group optionally substituted with at least one halogenatom, (7) a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, (8) a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom, (9) a C2-C6 dialkylaminogroup optionally substituted with at least one halogen atom and (10) aC2-C6 alkoxycarbonyl group optionally substituted with at least onehalogen atom” include a phenyl group, a 2-chlorophenyl group, a3-chlorophenyl group, a 4-chlorophenyl group, a 4-fluorophenyl group, a4-bromophenyl group, a 4-iodophenyl group, a 2-cyanophenyl group, a3-cyanophenyl group, a 4-cyanophenyl group, a 2-nitrophenyl group, a3-nitrophenyl group, a 4-nitrophenyl group, a 2-methylphenyl group, a3-methylphenyl group, a 4-methylphenyl group, a2-(trifluoromethyl)phenyl group, a 3-(trifluoromethyl)phenyl group, a4-(trifluoromethyl)phenyl group, a 2-methoxyphenyl group, a3-methoxyphenyl group, a 4-methoxyphenyl group, a4-(trifluoromethoxy)phenyl group, a 4-(methylthio)phenyl group, a4-(methylsulfinyl)phenyl group, a 4-(methylsulfonyl)phenyl group and a4-(methoxycarbonyl)phenyl group;

examples of the “naphthyl group optionally substituted with 1 to 9independent substituents selected from the group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom and (5) aC1-C6 alkoxy group optionally substituted with at least one halogenatom” include a 1-naphthyl and a 2-naphthyl group;

examples of the “5- to 6-membered heteroaryl group optionallysubstituted with one or more independent substituents selected from thegroup (1) a halogen atom, (2) a cyano group, (3) a nitro group, (4) aC1-C6 alkyl group optionally substituted with at least one halogen atomand (5) a C1-C6 alkoxy group optionally substituted with at least onehalogen atom” include a 1-methyl-2-pyrrolyl group, a 2-furyl group, a3-furyl group, a 5-bromo-2-furyl group, a 5-nitro-2-furyl group, a2-methyl-3-furyl group, a 2,5-dimethyl-3-furyl group, a2,4-dimethyl-3-furyl group, a 2-thienyl group, a 3-thienyl group, a5-methyl-2-thienyl group, a 3-methyl-2-thienyl group, a1-methyl-3-trifluoromethyl-5-pyrazolyl group, a5-chloro-1,3-dimethyl-4-pyrazolyl group, a 2-pyridinyl group, a3-pyridinyl group, a 4-pyridinyl group, a 2-methyl-3-pyridinyl group, a6-methyl-3-pyridinyl group, a 2-chloro-3-pyridinyl group, a6-chloro-3-pyridinyl group and a pyrazinyl group;

examples of the “3- to 8-membered non-aromatic heterocyclic groupoptionally substituted with one or more independent substituentsselected from a group consisting of (1) a halogen atom and (2) a C1-C6alkyl group” include a tetrahydro-2-furyl group, a tetrahydro-3-furylgroup, and a morpholino group;

examples of the “C7-C9 phenylalkyl group whose benzene ring moiety maybe substituted with 1 to 5 independent substituents selected from thegroup consisting of (1) a halogen atom, (2) a cyano group, (3) a nitrogroup, (4) a C1-C6 alkyl group optionally substituted with at least onehalogen atom and (5) a C1-C6 alkoxy group optionally substituted with atleast one halogen atom” include a benzyl group, a 1-phenylethyl group, a2-phenylethyl group, a 2-chlorobenzyl group, a 3-chlorobenzyl group, a4-chlorobenzyl group, a 2-cyanobenzyl group, a 3-cyanobenzyl group, a4-cyanobenzyl group, a 2-nitrobenzyl group, a 3-nitrobenzyl group, a4-nitrobenzyl group, a 2-methylbenzyl group, a 3-methylbenzyl group, a4-methylbenzyl group, a 2-(trifluoromethyl)benzyl group, a3-(trifluoromethyl)benzyl group, a 4-(trifluoromethyl)benzyl group, a2-methoxybenzyl group, a 3-methoxybenzyl group and a 4-methoxybenzylgroup; and

examples of the “C7-C9 phenoxyalkyl group whose benzene ring moiety maybe substituted with 1 to 5 independent substituents selected from thegroup consisting of (1) a halogen atom, (2) a cyano group, (3) a nitrogroup, (4) a C1-C6 alkyl group optionally substituted with at least onehalogen atom and (5) a C1-C6 alkoxy group optionally substituted with atleast one halogen atom” include a phenoxymethyl group, a 2-phenoxyethylgroup and a 1-phenoxyethyl group.

In R⁶ and R⁷, examples of the “C1-C6 alkyl group optionally substitutedwith at least one halogen atom” include a methyl group, an ethyl group,a 2,2,2-trifluoroethyl group, a 2,2,2-trichloroethyl group, a propylgroup, an isopropyl group, a butyl group, an isobutyl group, a sec-butylgroup, a tert-butyl group, a pentyl group and a hexyl group;

examples of the “C3-C6 alkoxyalkyl group optionally substituted with atleast one halogen atom” include a 2-methoxyethyl group, 2-ethoxyethylgroup and a 2-isopropyloxyethyl group;

examples of the “C2-C6 alkenyl group optionally substituted with atleast one halogen atom” include a 1-propenyl group, a 2-propenyl group,a 3-chloro-2-propenyl group, a 2-chloro-2-propenyl group, a3,3-dichloro-2-propenyl group, a 2-butenyl group, a 3-butenyl group, a2-methyl-2-propenyl group, a 3-methyl-2-butenyl group, a 2-pentenylgroup and a 2-hexenyl group;

examples of the “C3-C6 alkynyl group optionally substituted with atleast one halogen atom” include a 2-propynyl group, a3-chloro-2-propynyl group, a 3-bromo-2-propynyl group, a 2-butynyl groupand a 3-butynyl group;

examples of the “C3-C6 cycloalkyl group optionally substituted with oneor more independent substituents selected from the group consisting of(1) a halogen atom and (2) a C1-C6 alkyl group” include a cyclopropylgroup, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group;

examples of the “phenyl group optionally substituted with 1 to 5independent substituents selected from the group consisting of the (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom, (5) a C1-C6alkoxy group optionally substituted with at least one halogen atom, (6)a C1-C6 alkylthio group optionally substituted with at least one halogenatom, (7) a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, (8) a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom, (9) a C2-C6 dialkylaminogroup optionally substituted with at least one halogen atom and (10) aC2-C6 alkoxycarbonyl group optionally substituted with at least onehalogen atom” include a phenyl group, a 2-chlorophenyl group, a3-chlorophenyl group, a 4-chlorophenyl group, a 4-fluorophenyl group, a4-bromophenyl group, a 4-iodophenyl group, a 2-cyanophenyl group, a3-cyanophenyl group, a 4-cyanophenyl group, a 2-nitrophenyl group, a3-nitrophenyl group, a 4-nitrophenyl group, a 2-methylphenyl group, a3-methylphenyl group, a 4-methylphenyl group, a2-(trifluoromethyl)phenyl group, a 3-(trifluoromethyl)phenyl group, a4-(trifluoromethyl)phenyl group, a 2-methoxyphenyl group, a3-methoxyphenyl group, a 4-methoxyphenyl group, a4-(trifluoromethoxy)phenyl group, a 4-(methylthio)phenyl group, a4-(methylsulfinyl)phenyl group, a 4-(methylsulfonyl)phenyl group and a4-(methoxycarbonyl)phenyl group;

examples of the “5- to 6-membered heteroaryl group optionallysubstituted with 1 to 5 independent substituents selected from the groupconsisting of (1) a halogen atom, (2) a cyano group, (3) a nitro group,(4) a C1-C6 alkyl group optionally substituted with at least one halogenatom and (5) a C1-C6 alkoxy group optionally substituted with at leastone halogen atom” include a 2-pyridinyl group; and

examples of the “C7-C9 phenylalkyl group whose benzene ring moiety maybe substituted with 1 to 5 independent substituents selected from thegroup consisting of (1) a halogen atom, (2) a cyano group, (3) a nitrogroup, (4) a C1-C6 alkyl group optionally substituted with at least onehalogen atom and (5) a C1-C6 alkoxy group optionally substituted with atleast one halogen atom” include a benzyl group, a 1-phenylethyl group, a2-phenylethyl group, a 2-chlorobenzyl group, a 3-chlorobenzyl group, a4-chlorobenzyl group, a 2-cyanobenzyl group, a 3-cyanobenzyl group, a4-cyanobenzyl group, a 2-nitrobenzyl group, a 3-nitrobenzyl group, a4-nitrobenzyl group, a 2-methylbenzyl group, a 3-methylbenzyl group, a4-methylbenzyl group, a 2-(trifluoromethyl)benzyl group, a3-(trifluoromethyl)benzyl group, a 4-(trifluoromethyl)benzyl group, a2-methoxybenzyl group, a 3-methoxybenzyl group and a 4-methoxybenzylgroup.

In R⁸ and R⁹, examples of the “C1-C6 alkyl group optionally substitutedwith at least one halogen atom” include a methyl group, an ethyl group,a 2,2,2-trifluoroethyl group, a 2,2,2-trichloroethyl group, a propylgroup, an isopropyl group, a butyl group, an isobutyl group, a sec-butylgroup, a tert-butyl group, a pentyl group and a hexyl group;

examples of the “C2-C6 alkoxyalkyl group optionally substituted with atleast one halogen atom” include a 2-methoxyethyl group, a 2-ethoxyethylgroup and a 2-isopropyloxyethyl group;

examples of the “C2-C6 alkenyl group optionally substituted with atleast one halogen atom” include a 2-propenyl group, a3-chloro-2-propenyl group, a 2-chloro-2-propenyl group, a3,3-dichloro-2-propenyl group, a 2-butenyl group, a 3-butenyl group, a2-methyl-2-propenyl group, a 3-methyl-2-butenyl group, a 2-pentenylgroup and a 2-hexenyl group;

examples of the “C3-C6 alkynyl group optionally substituted with atleast one halogen atom” include a 2-propynyl group, a3-chloro-2-propynyl group, a 3-bromo-2-propynyl group, a 2-butynyl groupand a 3-butynyl group;

examples of the “C3-C6 cycloalkyl group optionally substituted with oneor more independent substituents selected from the group consisting of(1) a halogen atom and (2) a C1-C6 alkyl group include a cyclopropylgroup, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group;

examples of the “phenyl group optionally substituted with 1 to 5independent substituents selected from the group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom, (5) a C1-C6alkoxy group optionally substituted with at least one halogen atom, (6)a C1-C6 alkylthio group optionally substituted with at least one halogenatom, (7) a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, (8) a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom, (9) a C2-C6 dialkylaminogroup optionally substituted with at least one halogen atom and (10) aC2-C6 alkoxycarbonyl group optionally substituted with at least onehalogen atom” include a phenyl group, a 2-chlorophenyl group, a3-chlorophenyl group, a 4-chlorophenyl group, a 4-fluorophenyl group, a4-bromophenyl group, a 4-iodophenyl group, a 2-cyanophenyl group, a3-cyanophenyl group, a 4-cyanophenyl group, a 2-nitrophenyl group, a3-nitrophenyl group, a 4-nitrophenyl group, a 2-methylphenyl group, a3-methylphenyl group, a 4-methylphenyl group, a2-(trifluoromethyl)phenyl group, a 3-(trifluoromethyl)phenyl group, a4-(trifluoromethyl)phenyl group, a 2-methoxyphenyl group, a3-methoxyphenyl group, a 4-methoxyphenyl group, a4-(trifluoromethoxy)phenyl group, a 4-(methylthio)phenyl group, a4-(methylsulfinyl)phenyl group, a 4-(methylsulfonyl)phenyl group and a4-(methoxycarbonyl)phenyl group;

examples of the “5- to 6-membered heteroaryl group optionallysubstituted with 1 to 5 independent substituents selected from the groupconsisting of (1) a halogen atom, (2) a cyano group, (3) a nitro group,(4) a C1-C6 alkyl group optionally substituted with at least one halogenatom and (5) a C1-C6 alkoxy group optionally substituted with at leastone halogen atom” include a 3-pyridinyl group;

examples of the “C7-C9 phenylalkyl group whose benzene ring moiety maybe substituted with 1 to 5 independent substituents selected from thegroup consisting of (1) a halogen atom, (2) a cyano group, (3) a nitrogroup, (4) a C1-C6 alkyl group optionally substituted with at least onehalogen atom and (5) a C1-C6 alkoxy group optionally substituted with atleast one halogen atom” include a benzyl group, a 1-phenylethyl group, a2-phenylethyl group, a 2-chlorobenzyl group, a 3-chlorobenzyl group, a4-chlorobenzyl group, a 2-cyanobenzyl group, a 3-cyanobenzyl group, a4-cyanobenzyl group, a 2-nitrobenzyl group, a 3-nitrobenzyl group, a4-nitrobenzyl group, a 2-methylbenzyl group, a 3-methylbenzyl group, a4-methylbenzyl group, a 2-(trifluoromethyl)benzyl group, a3-(trifluoromethyl)benzyl group, a 4-(trifluoromethyl)benzyl group, a2-methoxybenzyl group, a 3-methoxybenzyl group and a 4-methoxybenzylgroup; and

examples of the “3- to 8-membered non-aromatic heterocyclic group” when“R⁸ and R⁹ are taken together with the nitrogen atom to which they arebound to form a 3- to 8-membered non-aromatic heterocyclic group”include a pyrrolidin-1-yl group, piperidino group, a3,5-dimethylpiperidino group, a hexamethyleneimin-1-yl group, aheptamethyleneimin-1-yl group, a morpholino group, a2,6-dimethylmorpholino group, a thiomorpholin-4-yl group, a4-methylpiperazin-1-yl group, a 4-(ethoxycarbonyl)piperazin-1-yl groupand a 4-phenylpiperazin-1-yl group.

In R¹⁰, examples of the “C1-C6 alkyl group optionally substituted withat least one halogen atom” include a methyl group, a trifluoromethylgroup, a trichloromethyl group, an ethyl group, a 2-chloroethyl group, a2,2,2-trifluoroethyl group, a propyl group, an isopropyl group, a butylgroup, an isobutyl group, a sec-butyl group, a tert-butyl group, apentyl group and a hexyl group;

examples of the “C3-C6 cycloalkyl group optionally substituted with oneor more independent substituents selected from the group consisting of(1) a halogen atom and (2) a C1-C6 alkyl group optionally substitutedwith at least one halogen atom” include a cyclopropyl group, acyclobutyl group, a cyclopentyl group and a cyclohexyl group; and

examples of the “phenyl group optionally substituted with 1 to 5independent substituents selected from the group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom and (5) aC1-C6 alkoxy group optionally substituted with at least one halogenatom” include a phenyl group, a 4-chlorophenyl group, a 4-nitrophenylgroup and a 4-methylphenyl group.

In R¹¹ and R¹², examples of the “C1-C6 alkyl group optionallysubstituted with at least one halogen atom” include a methyl group, anethyl group, a 2,2,2-trifluoroethyl group, a 2,2,2-trichloroethyl group,a propyl group, an isopropyl group, a butyl group, an isobutyl group, asec-butyl group, a tert-butyl group, a pentyl group and a hexyl group;

examples of the “C3-C6 cycloalkyl group optionally substituted with oneor more independent substituents selected from the group consisting of(1) a halogen atom and (2) a C1-C6 alkyl group optionally substitutedwith at least one halogen atom” include a cyclopropyl group, acyclobutyl group, a cyclopentyl group and a cyclohexyl group;

examples of the “phenyl group optionally substituted with 1 to 5independent groups selected from the group consisting of (1) a halogenatom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkyl groupoptionally substituted with at least one halogen atom and (5) a C1-C6alkoxy group optionally substituted with at least one halogen atom”include a phenyl group and a 4-methylphenyl group; and

examples of the “3- to 8-membered non-aromatic heterocyclic group” when“R¹¹ and R¹² are taken together with the nitrogen atom to which they arebound to form a 3- to 8-membered non-aromatic heterocyclic group”include a pyrrolidin-1-yl group, a piperidino group, a3,5-dimethylpiperidino group, a morpholino group, a2,6-dimethylmorpholino group, a thiomorpholin-4-yl group, a4-methylpiperazin-1-yl group, a 4-(ethoxycarbonyl)piperazin-1-yl groupand a 4-phenylpiperazin-1-yl group.

In R^(13a) and R^(13b), examples of the “C1-C6 alkyl group optionallysubstituted with at least one halogen atom” include a methyl group, afluoromethyl group, a difluoromethyl group, a trifluoromethyl group, anethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethylgroup, a propyl group, an isopropyl group, a butyl group, an isobutylgroup, a sec-butyl group, a tert-butyl group, a pentyl group and a hexylgroup;

examples of the “C2-C6 cyanoalkyl group” include a cyanomethyl group anda 2-cyanoethyl group;

examples of the “C2-C6 alkoxyalkyl group optionally substituted with atleast one halogen atom” include a methoxymethyl group, an ethoxymethylgroup, a 2-methoxyethyl group, a 2-ethoxyethyl group and a2-isopropyloxyethyl group;

examples of the “C2-C6 alkenyl group optionally substituted with atleast one halogen atom” include a 2-propenyl group, a3-chloro-2-propenyl group, a 2-chloro-2-propenyl group, a3,3-dichloro-2-propenyl group, a 2-butenyl group, a 3-butenyl group, a2-methyl-2-propenyl group, a 3-methyl-2-butenyl group, a 2-pentenylgroup and a 2-hexenyl group;

examples of the “C2-C6 alkynyl group optionally substituted with atleast one halogen atom” include a 2-propynyl group, a3-chloro-2-propynyl group, a 3-bromo-2-propynyl group, a 2-butynyl groupand a 3-butynyl group;

examples of the “C3-C6 cycloalkyl group optionally substituted with oneor more independent substituents selected from the group consisting of(1) a halogen atom and (2) a C1-C6 alkyl group” include a cyclopropylgroup, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group;

examples of the “phenyl group optionally substituted with 1 to 5independent substituents selected from a group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom, (5) a C1-C6alkoxy group optionally substituted with at least one halogen atom, (6)a C1-C6 alkylthio group optionally substituted with at least one halogenatom, (7) a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom and (8) a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom” include a phenyl group, a2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a2-chlorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a2-bromophenyl group, a 2-iodophenyl group, a 2,6-difluorophenyl group, a2,6-dichlorophenyl group, a 2-chloro-6-fluorophenyl group, a2-chloro-4-fluorophenyl group, a 2-cyanophenyl group, a 3-cyanophenylgroup, a 4-cyanophenyl group, a 2-nitrophenyl group, a 3-nitrophenylgroup, a 4-nitrophenyl group, a 2-methylphenyl group, a 3-methylphenylgroup, a 4-methylphenyl group, a 2-ethylphenyl group, a2-isopropylphenyl group, a 2-tert-butylphenyl group, a2-(trifluoromethyl)phenyl group, a 3-(trifluoromethyl)phenyl group, a4-(trifluoromethyl)phenyl group, a 2-methoxyphenyl group, a3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-ethoxyphenyl group,a 2-(trifluoromethoxy)phenyl group, a 2-(methylthio)phenyl group, a2-(methylsulfinyl)phenyl group and a 2-(methylsulfonyl)phenyl group;

examples of the “5- to 6-membered heteroaryl group optionallysubstituted with one or more independent substituents selected from thegroup consisting of (1) a halogen atom, (2) a cyano group, (3) a nitrogroup, (4) a C1-C6 alkyl group optionally substituted with at least onehalogen atom and (5) a C1-C6 alkoxy group optionally substituted with atleast one halogen atom” include a 2-pyridinyl group, a3-fluoro-2-pyridinyl group, a 3-chloro-2-pyridinyl group, a3-bromo-2-pyridinyl group, a 3-iodo-2-pyridinyl group, a3-methyl-2-pyridinyl group, a 3-trifluoromethyl-2-pyridinyl group, a3-methoxy-2-pyridinyl group, a 3-cyano-2-pyridinyl group, a3-nitro-2-pyridinyl group, a 3-pyridinyl group, a 2-chloro-3-pyridinylgroup, a 4-chloro-3-pyridinyl group, a 4-pyridinyl group, a3-chloro-4-pyridinyl group, a 3,5-dichloro-4-pyridinyl group, a2-pyrimidinyl group, a 4-methyl-2-pyrimidinyl group, a4,6-dimethyl-2-pyrimidinyl group, a 4-pyrimidinyl group, a5-chloro-4-pyrimidinyl group, a pyrazinyl group, a 3-methyl-2-pyrazinylgroup, a 2-thiazolyl group, a 1-methyl-5-pyrazolyl group, a4-chloro-1-methyl-5-pyrazolyl group, a 4-chloro-1,3-dimethyl-5-pyrazolylgroup and a 4-chloro-5-methyl-3-isooxazolyl group;

examples of the “C7-C9 phenylalkyl group whose benzene ring moiety maybe substituted with one or more independent substituents selected fromthe group consisting of (1) a halogen atom, (2) a cyano group, (3) anitro group, (4) a C1-C6 alkyl group optionally substituted with atleast one halogen atom and (5) a C1-C6 alkoxy group optionallysubstituted with at least one halogen atom” include a benzyl group, a1-phenylethyl group, a 2-phenylethyl group, a 2-chlorobenzyl group, a3-chlorobenzyl group, a 4-chlorobenzyl group, a 2-cyanobenzyl group, a3-cyanobenzyl group, a 4-cyanobenzyl group, a 2-nitrobenzyl group, a3-nitrobenzyl group, a 4-nitrobenzyl group, a 2-methylbenzyl group, a3-methylbenzyl group, a 4-methylbenzyl group, a2-(trifluoromethyl)benzyl group, a 3-(trifluoromethyl)benzyl group, a4-(trifluoromethyl)benzyl group, a 2-methoxybenzyl group, a3-methoxybenzyl group and a 4-methoxybenzyl group; and

examples of the “C7-C9 pyridinylalkyl group whose pyridine ring moietymay be substituted with one or more independent substituents selectedfrom the group consisting of (1) a halogen atom, (2) a cyano group, (3)a nitro group, (4) a C1-C6 alkyl group optionally substituted with atleast one halogen atom and (5) a C1-C6 alkoxy group optionallysubstituted with at least one halogen atom” include a 2-pyridinylmethylgroup, a 3-pyridinylmethyl group, a 4-pyridinylmethyl group, a3-chloro-2-pyridinylmethyl group, and a 2-chloro-3-pyridinylmethylgroup.

In R^(14a) and R^(14b), examples of the “C1-C6 alkyl group optionallysubstituted with at least one halogen atom” include a methyl group, atrifluoromethyl group, a trichloromethyl group, a chloromethyl group, adichloromethyl group, a fluoromethyl group, a difluoromethyl group, anethyl group, a pentafluoroethyl group, a propyl group, an isopropylgroup, a butyl group, an isobutyl group, a sec-butyl group, a tert-butylgroup, a pentyl group and a hexyl group;

examples of the “C1-C6 alkoxy group optionally substituted with at leastone halogen atom” include a methoxy group, an ethoxy group, a2,2,2-trifluoroethoxy group, a propoxy group, an isopropyloxy group, abutoxy group, an isobutyloxy group, a sec-butoxy group and a tert-butoxygroup;

examples of the “C2-C6 cyanoalkyloxy group” include a cyanomethoxy groupand a 2-cyanoethoxy group;

examples of the “C3-C6 alkoxyalkyloxy group optionally substituted withat least one halogen atom” include a 2-(methoxy)ethoxy group;

examples of the “C3-C6 alkenyloxy group optionally substituted with atleast one halogen atom” include a 2-propenyloxy group and a2-methyl-2-propenyloxy group;

examples of the “C3-C6 alkynyloxy group optionally substituted with atleast one halogen atom” include a 2-propynyloxy group and a 2-butynyloxygroup;

examples of the “C1-C6 alkylthio group optionally substituted with atleast one halogen atom” include a methylthio group, atrifluoromethylthio group, an ethylthio group, a propylthio group, anisopropylthio group, a butylthio group, an isobutylthio group, asec-butylthio group, a tert-butylthio group, a pentylthio group and ahexylthio group;

examples of the “C1-C6 alkylsulfinyl group optionally substituted withat least one halogen atom” include a methylsulfinyl group, atrifluoromethylsulfinyl group, an ethylsulfinyl group, a propylsulfinylgroup, an isopropylsulfinyl group, a butylsulfinyl group, anisobutylsulfinyl group, a sec-butylsulfinyl group, a tert-butylsulfinylgroup, a pentylsulfinyl group and a hexylsulfinyl group;

examples of the “C1-C6 alkylsulfonyl group optionally substituted withat least one halogen atom” include a methylsulfonyl group, atrifluoromethylsulfonyl group, an ethylsulfonyl group, a propylsulfonylgroup, an isopropylsulfonyl group, a butylsulfonyl group, anisobutylsulfonyl group, a sec-butylsulfonyl group, a tert-butylsulfonylgroup, a pentylsulfonyl group and a hexylsulfonyl group;

examples of the “phenyl group optionally substituted with 1 to 5independent substituents selected from the group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom and (5) aC1-C6 alkoxy group optionally substituted with at least one halogenatom” include a phenyl group, a 2-chlorophenyl group, a 3-chlorophenylgroup, a 4-chlorophenyl group, a 4-fluorophenyl group, a 4-bromophenylgroup, a 4-iodophenyl group, a 2-cyanophenyl group, a 3-cyanophenylgroup, a 4-cyanophenyl group, a 2-nitrophenyl group, a 3-nitrophenylgroup, a 4-nitrophenyl group, a 2-methylphenyl group, a 3-methylphenylgroup, a 4-methylphenyl group, a 2-(trifluoromethyl)phenyl group, a3-(trifluoromethyl)phenyl group, a 4-(trifluoromethyl)phenyl group, a2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl groupand a 4-(trifluoromethoxy)phenyl group;

examples of the “5- to 6-membered heteroaryl group optionallysubstituted with one or more independent substituents selected from thegroup consisting of (1) a halogen atom, (2) a cyano group, (3) a nitrogroup, (4) a C1-C6 alkyl group optionally substituted with at least onehalogen atom and (5) a C1-C6 alkoxy group optionally substituted with atleast one halogen atom” include a 2-furyl group, a 3-furyl group, a2-pyridinyl group, a 3-pyridinyl group, a 4-pyridinyl group and apyrazinyl group; and

examples of the “phenoxy group optionally substituted with 1 to 5independent substituents selected from the group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom and (5) aC1-C6 alkoxy group optionally substituted with at least one halogenatom” include a phenoxy group, a 2-chlorophenoxy group, a3-chlorophenoxy group, a 4-chlorophenoxy group, a 2-cyanophenoxy group,a 3-cyanophenoxy group, a 4-cyanophenoxy group, a 2-nitrophenoxy group,a 3-nitrophenoxy group, a 4-nitrophenoxy group, a 2-methylphenoxy group,a 3-methylphenoxy group, a 4-methylphenoxy group, a2-(trifluoromethyl)phenoxy group, a 3-(trifluoromethyl)phenoxy group, a4-(trifluoromethyl)phenoxy group, a 2-methoxyphenoxy group, a3-methoxyphenoxy group, a 4-methoxyphenoxy group and a4-(trifluoromethoxy)phenoxy group.

Examples of the group represented by J1 include a 1-phenylpyrazol-5-ylgroup, a 1-(2-chlorophenyl)pyrazol-5-yl group, a1-(2-pyridinyl)pyrazol-5-yl group, a1-(3-chloro-2-pyridinyl)pyrazol-5-yl, a 3-fluoro-1-phenylpyrazol-5-ylgroup, a 1-(2-chlorophenyl)-3-fluoropyrazol-5-yl group, a3-fluoro-1-(2-pyridinyl)pyrazol-5-yl group, a3-fluoro-1-(3-chloro-2-pyridinyl)pyrazol-5-yl group, a3-chloro-1-phenylpyrazol-5-yl group, a3-chloro-1-(2-chlorophenyl)pyrazol-5-yl group, a3-chloro-1-(2-pyridinyl)pyrazol-5-yl group, a3-chloro-1-(3-chloro-2-pyridinyl)pyrazol-5-yl group, a3-bromo-1-phenylpyrazol-5-yl group, a3-bromo-1-(2-chlorophenyl)pyrazol-5-yl group, a3-bromo-1-(2-pyridinyl)pyrazol-5-yl group, a3-bromo-1-(3-chloro-2-pyridinyl)pyrazol-5-yl group, a3-iodo-1-phenylpyrazol-5-yl group, a3-iodo-1-(2-chlorophenyl)pyrazol-5-yl group, a3-iodo-1-(2-pyridinyl)pyrazol-5-yl group, a3-iodo-1-(3-chloro-2-pyridinyl)pyrazol-5-yl group, a3-methyl-1-phenylpyrazol-5-yl group, a1-(2-chlorophenyl)-3-methylpyrazol-5-yl group, a3-methyl-1-(2-pyridinyl)pyrazol-5-yl group, a1-(3-chloro-2-pyridinyl)-3-methylpyrazol-5-yl group, a1-phenyl-3-(trifluoromethyl)pyrazol-5-yl group, a1-(2-chlorophenyl)-3-(trifluoromethyl)pyrazol-5-yl group, a1-(2-pyridinyl)-3-(trifluoromethyl)pyrazol-5-yl group, a1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)pyrazol-5-yl group,

a 3-chloro-1-methylpyrazol-5-yl group, a 3-chloro-1-ethylpyrazol-5-ylgroup, a 3-chloro-1-isopropylpyrazol-5-yl group, a1-tert-butyl-3-chloropyrazol-5-yl group, a3-chloro-1-(3-fluoro-2-pyridinyl)pyrazol-5-yl group, a1-(3-bromo-2-pyridinyl)-3-chloropyrazol-5-yl group, a3-chloro-1-(3-iodo-2-pyridinyl)pyrazol-5-yl group, a3-chloro-1-(3-methyl-2-pyridinyl)pyrazol-5-yl group, a3-chloro-1-(3-trifluoromethyl-2-pyridinyl)pyrazol-5-yl group, a3-chloro-1-(3-methoxy-2-pyridinyl)pyrazol-5-yl group, a3-chloro-1-(3-cyano-2-pyridinyl)pyrazol-5-yl group, a3-chloro-1-(3-nitro-2-pyridinyl)pyrazol-5-yl group,

a 3-bromo-1-methylpyrazol-5-yl group, a 3-bromo-1-ethylpyrazol-5-ylgroup, a 3-bromo-1-isopropylpyrazol-5-yl group, a3-bromo-1-tert-butylpyrazol-5-yl group, a3-bromo-1-(3-fluoro-2-pyridinyl)pyrazol-5-yl group, a3-bromo-1-(3-bromo-2-pyridinyl)pyrazol-5-yl group, a3-bromo-1-(3-iodo-2-pyridinyl)pyrazol-5-yl group, a3-bromo-1-(3-methyl-2-pyridinyl)pyrazol-5-yl group, a3-bromo-1-(3-trifluoromethyl-2-pyridinyl)pyrazol-5-yl group, a3-bromo-1-(3-methoxy-2-pyridinyl)pyrazol-5-yl group, a3-bromo-1-(3-cyano-2-pyridinyl)pyrazol-5-yl group, a3-bromo-1-(3-nitro-2-pyridinyl)pyrazol-5-yl group,

a 1-methyl-3-(trifluoromethyl)pyrazol-5-yl group, a1-ethyl-3-(trifluoromethyl)pyrazol-5-yl group, a1-isopropyl-3-(trifluoromethyl)pyrazol-5-yl group, a1-tert-butyl-3-(trifluoromethyl)pyrazol-5-yl group, a1-(3-fluoro-2-pyridinyl)-3-(trifluoromethyl)pyrazol-5-yl group, a1-(3-bromo-2-pyridinyl)-3-(trifluoromethyl)pyrazol-5-yl group, a1-(3-iodo-2-pyridinyl)-3-(trifluoromethyl)pyrazol-5-yl group, a1-(3-methyl-2-pyridinyl)-3-(trifluoromethyl)pyrazol-5-yl group, a1-(3-trifluoromethyl-2-pyridinyl)-3-(trifluoromethyl)pyrazol-5-yl group,a 1-(3-methoxy-2-pyridinyl)-3-(trifluoromethyl)pyrazol-5-yl group, a1-(3-cyano-2-pyridinyl)-3-(trifluoromethyl)pyrazol-5-yl group, a1-(3-nitro-2-pyridinyl)-3-(trifluoromethyl)pyrazol-5-yl group,

a 1-(3-chloro-2-pyridinyl)-3-ethylpyrazol-5-yl group, a1-(3-chloro-2-pyridinyl)-3-isopropylpyrazol-5-yl group, a3-tert-butyl-1-(3-chloro-2-pyridinyl)pyrazol-5-yl group, a1-(3-chloro-2-pyridinyl)-3-(methylthio)pyrazol-5-yl group, a1-(3-chloro-2-pyridinyl)-3-(ethylthio)pyrazol-5-yl group, a1-(3-chloro-2-pyridinyl)-3-(isopropylthio)pyrazol-5-yl group, a3-tert-butylthio-1-(3-chloro-2-pyridinyl)pyrazol-5-yl group, a1-(3-chloro-2-pyridinyl)-3-(methylsulfinyl)pyrazol-5-yl group, a1-(3-chloro-2-pyridinyl)-3-(ethylsulfinyl)pyrazol-5-yl group, a1-(3-chloro-2-pyridinyl)-3-(isopropylsulfinyl)pyrazol-5-yl group, a3-tert-butylsulfinyl-1-(3-chloro-2-pyridinyl)pyrazol-5-yl group, a1-(3-chloro-2-pyridinyl)-3-(methylsulfonyl)pyrazol-5-yl group, a1-(3-chloro-2-pyridinyl)-3-(ethylsulfonyl)pyrazol-5-yl group, a1-(3-chloro-2-pyridinyl)-3-(isopropylsulfonyl)pyrazol-5-yl group, a3-tert-butylsulfonyl-1-(3-chloro-2-pyridinyl)pyrazol-5-yl group, a1-(3-chloro-2-pyridinyl)-3-(2,2,2-trifluoroethoxy)pyrazol-5-yl group, a1-(3-chloro-2-pyridinyl)-3-cyanopyrazol-5-yl group,

a 1-(2-chlorophenyl)pyrrol-2-yl group, a1-(3-chloro-2-pyridinyl)pyrrol-2-yl group, a4-chloro-1-(2-chlorophenyl)pyrrol-2-yl group, a4-chloro-1-(3-chloro-2-pyridinyl)pyrrol-2-yl group, a5-chloro-1-(2-chlorophenyl)pyrrol-2-yl group, a5-chloro-1-(3-chloro-2-pyridinyl)pyrrol-2-yl group, a1-(2-chlorophenyl)-4,5-dichloropyrrol-2-yl group, a1-(3-chloro-2-pyridinyl)-4,5-dichloropyrrol-2-yl group, a4-bromo-1-(2-chlorophenyl)pyrrol-2-yl group, a4-bromo-1-(3-chloro-2-pyridinyl)pyrrol-2-yl group, a5-bromo-1-(2-chlorophenyl)pyrrol-2-yl group, a5-bromo-1-(3-chloro-2-pyridinyl)pyrrol-2-yl group, a1-(2-chlorophenyl)-4,5-dibromopyrrol-2-yl group, a1-(3-chloro-2-pyridinyl)-4,5-dibromopyrrol-2-yl group, a1-(2-chlorophenyl)-4-iodopyrrol-2-yl group, a1-(3-chloro-2-pyridinyl)-4-iodopyrrol-2-yl group, a1-(2-chlorophenyl)-5-iodopyrrol-2-yl group, a1-(3-chloro-2-pyridinyl)-5-iodopyrrol-2-yl group, a1-(2-chlorophenyl)-4,5-diiodopyrrol-2-yl group, a1-(3-chloro-2-pyridinyl)-4,5-diiodopyrrol-2-yl group, a1-(2-chlorophenyl)-4-(trifluoromethyl)pyrrol-2-yl group, a1-(3-chloro-2-pyridinyl)-4-(trifluoromethyl)pyrrol-2-yl group, a1-(2-chlorophenyl)-5-(trifluoromethyl)pyrrol-2-yl group, a1-(3-chloro-2-pyridinyl)-5-(trifluoromethyl)pyrrol-2-yl group,

a 1-(2-chlorophenyl)imidazol-2-yl group, a1-(3-chloro-2-pyridinyl)imidazol-2-yl group, a4-chloro-1-(2-chlorophenyl)imidazol-2-yl group, a4-chloro-1-(3-chloro-2-pyridinyl)imidazol-2-yl group, a4-bromo-1-(2-chlorophenyl)imidazol-2-yl group, a4-bromo-1-(3-chloro-2-pyridinyl)imidazol-2-yl group, a1-(2-chlorophenyl)-4-(trifluoromethyl)imdazol-2-yl group, a1-(3-chloro-2-pyridinyl)-4-(trifluoromethyl)imidazol-2-yl group,

a 1-(2-chlorophenyl)-1,2,4-triazol-5-yl group, a1-(3-chloro-2-pyridinyl)-1,2,4-triazol-5-yl group, a3-chloro-1-(2-chlorophenyl)-1,2,4-triazol-5-yl group, a3-chloro-1-(3-chloro-2-pyridinyl)-1,2,4-triazol-5-yl group, a3-bromo-1-(2-chlorophenyl)-1,2,4-triazol-5-yl group, a3-bromo-1-(3-chloro-2-pyridinyl)-1,2,4-triazol-5-yl group, a1-(2-chlorophenyl)-3-(trifluoromethyl)-1,2,4-triazol-5-yl group and a1-(3-chloro-2-pyridinyl)-3-(trifluoromethyl)-1,2,4-triazol-5-yl group.

Examples of the group represented by J2 include a1-methyl-3-phenylpyrazol-4-yl group, a3-(2-chlorophenyl)-1-methylpyrazol-4-yl group, a1-methyl-3-(2-pyridinyl)pyrazol-4-yl group, a3-(3-chloro-2-pyridinyl)-1-methylpyrazol-4-yl group, a1-methyl-5-phenylpyrazol-4-yl group, a5-(2-chlorophenyl)-1-methylpyrazol-4-yl group, a1-methyl-5-(2-pyridinyl)pyrazol-4-yl group, a5-(3-chloro-2-pyridinyl)-1-methylpyrazol-4-yl group, a3-phenyl-1-(2,2,2-trifluoroethyl)pyrazol-4-yl group, a3-(2-chlorophenyl)-1-(2,2,2-trifluoroethyl)pyrazol-4-yl group, a3-(2-pyridinyl)-1-(2,2,2-trifluoroethyl)pyrazol-4-yl group, a3-(3-chloro-2-pyridinyl)-1-(2,2,2-trifluoroethyl)pyrazol-4-yl group, a5-phenyl-1-(2,2,2-trifluoroethyl)pyrazol-4-yl group, a5-(2-chlorophenyl)-1-(2,2,2-trifluoroethyl)pyrazol-4-yl group, a5-(2-pyridinyl)-1-(2,2,2-trifluoroethyl)pyrazol-4-yl group, a5-(3-chloro-2-pyridinyl)-1-(2,2,2-trifluoroethyl)pyrazol-4-yl group, a1-(difluoromethyl)-3-phenylpyrazol-4-yl group, a3-(2-chlorophenyl)-1-(difluoromethyl)pyrazol-4-yl group, a1-(difluoromethyl)-3-(2-pyridinyl)pyrazol-4-yl group, a3-(3-chloro-2-pyridinyl)-1-(difluoromethyl)pyrazol-4-yl group, a1-(difluoromethyl)-5-phenylpyrazol-4-yl group, a5-(2-chlorophenyl)-1-(difluoromethyl)pyrazol-4-yl group, a1-(difluoromethyl)-5-(2-pyridinyl)pyrazol-4-yl group, a5-(3-chloro-2-pyridinyl)-1-(difluoromethyl)pyrazol-4-yl group, a3-(2-chlorophenyl)-1-ethylpyrazol-4-yl group, a3-(3-chloro-2-pyridinyl)-1-ethylpyrazol-4-yl group, a5-(2-chlorophenyl)-1-ethylpyrazol-4-yl group, a5-(3-chloro-2-pyridinyl)-1-ethylpyrazol-4-yl group, a3-(2-chlorophenyl)-1-isopropylpyrazol-4-yl group, a3-(3-chloro-2-pyridinyl)-1-isopropylpyrazol-4-yl group, a5-(2-chlorophenyl)-1-isopropylpyrazol-4-yl group, a5-(3-chloro-2-pyridinyl)-1-isopropylpyrazol-4-yl group, a3-(2-chlorophenyl)-1-tert-butylpyrazol-4-yl group, a3-(3-chloro-2-pyridinyl)-1-tert-butylpyrazol-4-yl group, a5-(2-chlorophenyl)-1-tert-butylpyrazol-4-yl group and a5-(3-chloro-2-pyridinyl)-1-tert-butylpyrazol-4-yl group.

As an example of the compound represented by the formula (1), thefollowing compound is mentioned:

A compound of the formula (1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R⁴ is a halogen atom, a cyano group, a C1-C6 alkyl group optionallysubstituted with at least one halogen atom, a C1-C6 alkoxy groupoptionally substituted with at least one halogen atom, a phenyl groupoptionally substituted with at least one halogen atom, or

two R⁴ groups which are bound to the adjacent carbon atoms are bound toeach other at their terminal ends to form a group

T1: —CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ represent a hydrogen atom),

n is an integer of 0 to 3,

Q is a group represented by Q1 to Q6:

Q1: —C(=A³¹)-R⁵ Q2: —C(=A³²)-OR⁶ Q3: —C(=A³³)-SR⁷ Q4: —C(=A³⁴)-NR⁸R⁹ Q5:—S(O)₂—R¹⁰ Q6: —S(O)₂—NR¹¹R¹²

(wherein A³¹, A³² and A³³ are an oxygen atom, A³⁴ is an oxygen atom or asulfur atom,

R⁵ is a hydrogen atom; a C1-C6 alkyl group optionally substituted withone or more independent substituents selected from the group consistingof (1) a halogen atom, (2) a C1-C6 alkoxy group, (3) a C1-C6 alkylthiogroup, (4) a C1-C6 alkylsulfinyl group, (5) a C1-C6 alkylsulfonyl group,(6) a C2-C6 dialkylamino group and (7) a C3-C6 cycloalkyl group; a C3-C6cycloalkyl group optionally substituted with one or more independentsubstituents selected from the group consisting of (1) a halogen atomand (2) a C1-C6 alkyl group; a phenyl group optionally substituted with1 to 5 independent substituents selected from the group consisting of(1) a halogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6alkyl group optionally substituted with at least one halogen atom, (5) aC1-C6 alkoxy group optionally substituted with at least one halogenatom, (6) a C1-C6 alkylthio group optionally substituted with at leastone halogen atom, (7) a C1-C6 alkylsulfinyl group optionally substitutedwith at least one halogen atom, (8) a C1-C6 alkylsulfonyl groupoptionally substituted with at least one halogen atom, (9) a C2-C6dialkylamino group optionally substituted with at least one halogen atomand (10) a C2-C6 alkoxycarbonyl group optionally substituted with atleast one halogen atom; a 5 to 6-membered heteroaryl group optionallysubstituted with one or more independent substituents selected from thegroup consisting of (1) a halogen atom, (2) a cyano group, (3) a nitrogroup, (4) a C1-C6 alkyl group optionally substituted with at least onehalogen atom and (5) a C1-C6 alkoxy group optionally substituted with atleast one halogen atom; or a 3- to 8-membered non-aromatic heterocyclicgroup optionally substituted with one or more independent substituentsselected from the group consisting of (1) a halogen atom and (2) a C1-C6alkyl group,

R⁶ is a C1-C6 alkyl group optionally substituted with at least onehalogen atom; a C2-C6 alkenyl group optionally substituted with at leastone halogen atom; or a phenyl group optionally substituted with 1 to 5independent substituents selected from the group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom, (5) a C1-C6alkoxy group optionally substituted with at least one halogen atom, (6)a C1-C6 alkylthio group optionally substituted with at least one halogenatom, (7) a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, (8) a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom, (9) a C2-C6 dialkylaminogroup optionally substituted with at least one halogen atom and (10) aC2-C6 alkoxycarbonyl group optionally substituted with at least onehalogen atom,

R⁷ is a C1-C6 alkyl group optionally substituted with at least onehalogen atom,

R⁸ and R⁹ are independently a hydrogen atom; a C1-C6 alkyl groupoptionally substituted with at least one halogen atom; or a phenyl groupoptionally substituted with 1 to 5 independent substituents selectedfrom the group consisting of (1) a halogen atom, (2) a cyano group, (3)a nitro group, (4) a C1-C6 alkyl group optionally substituted with atleast one halogen atom, (5) a C1-C6 alkoxy group optionally substitutedwith at least one halogen atom, (6) a C1-C6 alkylthio group optionallysubstituted with at least one halogen atom, (7) a C1-C6 alkylsulfinylgroup optionally substituted with at least one halogen atom, (8) a C1-C6alkylsulfonyl group optionally substituted with at least one halogenatom, (9) a C2-C6 dialkylamino group optionally substituted with atleast one halogen atom and (10) a C2-C6 alkoxycarbonyl group optionallysubstituted with at least one halogen atom,

R¹⁰ is a C1-C6 alkyl group optionally substituted with at least onehalogen atom,

R¹¹ and R¹² are independently a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

J is a group represented by J1 or J2:

(wherein X^(a) is CH or a nitrogen atom, Y^(a) is CH, Z^(a) is CH or anitrogen atom, X^(b) is CH or a nitrogen atom, Y^(b) is CH, and Z^(b) isCH or a nitrogen atom,

R^(13a) is a C1-C6 alkyl group optionally substituted with at least onehalogen atom; a C3-C6 cycloalkyl group optionally substituted with oneor more independent substituents selected from the group consisting of(1) a halogen atom and (2) a C1-C6 alkyl group; a phenyl groupoptionally substituted with 1 to 5 independent substituents selectedfrom the group consisting of (1) a halogen atom, (2) a cyano group, (3)a nitro group, (4) a C1-C6 alkyl group optionally substituted with atleast one halogen atom, (5) a C1-C6 alkoxy group optionally substitutedwith at least one halogen atom, (6) a C1-C6 alkylthio group optionallysubstituted with at least one halogen atom, (7) a C1-C6 alkylsulfinylgroup optionally substituted with at least one halogen atom and (8) aC1-C6 alkylsulfonyl group optionally substituted with at least onehalogen atom; or a 5- to 6-membered heteroaryl group optionallysubstituted with one or more independent substituents selected from thegroup consisting of (1) a halogen atom, (2) a cyano group, (3) a nitrogroup, (4) a C1-C6 alkyl group optionally substituted with at least onehalogen atom and (5) a C1-C6 alkoxy group optionally substituted with atleast one halogen atom,

R^(13b) is a C1-C6 alkyl group optionally substituted with at least onehalogen atom,

R^(14a) is a halogen atom; a cyano group; a C1-C6 alkyl group optionallysubstituted with at least one halogen atom; a C1-C6 alkylthio groupoptionally substituted with at least one halogen atom; a C1-C6alkylsulfinyl group optionally substituted with at least one halogenatom; a C1-C6 alkylsulfonyl group optionally substituted with at leastone halogen atom; or a phenyl group optionally substituted with 1 to 5independent substituents selected from the group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom and (5) aC1-C6 alkoxy group optionally substituted with at least one halogenatom,

R^(14b) is a C1-C6 alkyl group optionally substituted with at least onehalogen atom; or a phenyl group optionally substituted with 1 to 5independent substituents selected from the group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom and (5) aC1-C6 alkoxy group optionally substituted with at least one halogenatom,

p is an integer of 0 to 2,

q is 1,

(provided that when p is 2, two R^(14a)'s may be the same ordifferent)), and

A¹ and A² are an oxygen atom.

Examples of the specific aspects of the present compound include thefollowing “Aspects 1 to 32”:

“Aspect 1”

A compound of the formula (1-1):

wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a hydrogen atom, a halogen atom, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom, a C1-C6 alkoxygroup optionally substituted with at least one halogen atom, or a phenylgroup optionally substituted with at least one halogen atom,

R^(4b), R^(4c) and R^(4d) are independently a hydrogen atom, a halogenatom, a cyano group, or a C1-C6 alkyl group optionally substituted withat least one halogen atom, or R^(4b) and R^(4c) are bound to each otherat their terminal ends to form a group:

—CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ are a hydrogen atom),

M is R⁵, OR⁶, SR⁷, or NR⁸R⁹

(wherein

R⁵ is a hydrogen atom; a C1-C6 alkyl group optionally substituted withat least one halogen atom; a C3-C6 cycloalkyl group; a phenyl groupoptionally substituted with one substituent selected from the groupconsisting of (1) a C1-C6 alkyl group optionally substituted with atleast one halogen atom and (2) a C1-C6 alkoxy group optionallysubstituted with at least one halogen atom; a 5 to 6-membered heteroarylgroup; or a 3- to 8-membered non-aromatic heterocyclic group,

R⁶ is a C1-C6 alkyl group optionally substituted with at least onehalogen atom, a C2-C6 alkenyl group optionally substituted with at leastone halogen atom, or a phenyl group,

R⁷ is a C1-C6 alkyl group optionally substituted with at least onehalogen atom,

R⁸ and R⁹ are independently a hydrogen atom, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom, or a phenylgroup, or R⁸ and R⁹ are taken together with the nitrogen atom to whichthey are bound to form a morpholino group),

X^(a) is a nitrogen atom,

R^(14ay) is a hydrogen atom, a halogen atom, a cyano group, a C1-C6alkyl group optionally substituted with at least one halogen atom, aC1-C6 alkylthio group optionally substituted with at least one halogenatom, a C1-C6 alkylsulfinyl group optionally substituted with at leastone halogen atom, a C1-C6 alkylsulfonyl group optionally substitutedwith at least one halogen atom, or a phenyl group,

R^(14az) is a hydrogen atom,

X¹⁸ is a nitrogen atom or CR^(18e)

(wherein R^(18e) is a hydrogen atom or a halogen atom), and

R^(18a), R^(18b), R^(18c) and R^(18d) are independently a hydrogen atomor a halogen atom.

“Aspect 2”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a hydrogen atom, a halogen atom, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom, a C1-C6 alkoxygroup optionally substituted with at least one halogen atom, or a phenylgroup optionally substituted with at least one halogen atom,

R^(4b), R^(4c) and R^(4d) are independently a hydrogen atom, a halogenatom, a cyano group, or a C1-C6 alkyl group optionally substituted withat least one halogen atom,

or R^(4b) and R^(4c) are bound to each other at their terminal ends toform a group; —CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ are a hydrogen atom),

M is R⁵, OR⁶, SR⁷, or NR⁸R⁹

(wherein R⁵ is a hydrogen atom; a C1-C6 alkyl group optionallysubstituted with at least one halogen atom; a C3-C6 cycloalkyl group; aphenyl group optionally substituted with one substituent selected fromthe group consisting of (1) a C1-C6 alkyl group optionally substitutedwith at least one halogen atom and (2) a C1-C6 alkoxy group optionallysubstituted with at least one halogen atom; a 5 to 6-membered heteroarylgroup; or a 3- to 8-membered non-aromatic heterocyclic group,

R⁶ is a C1-C6 alkyl group optionally substituted with at least onehalogen atom, a C2-C6 alkenyl group optionally substituted with at leastone halogen atom, or a phenyl group,

R⁷ is a C1-C6 alkyl group optionally substituted with at least onehalogen atom,

R⁸ and R⁹ are independently a hydrogen atom, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom, or a phenylgroup,

or R⁸ and R⁹ are taken together with the nitrogen atom to which they arebound to form a morpholino group),

X^(a) is CR^(14ax)

(wherein R^(14ax) is a hydrogen atom; a halogen atom; a cyano group; aC1-C6 alkyl group optionally substituted with at least one halogen atom;a C1-C6 alkylthio group optionally substituted with at least one halogenatom; or a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom, or a phenyl group),

R^(14ay) is a hydrogen atom; a halogen atom; a cyano group; a C1-C6alkyl group optionally substituted with at least one halogen atom; aC1-C6 alkylthio group optionally substituted with at least one halogenatom; a C1-C6 alkylsulfinyl group optionally substituted with at leastone halogen atom; a C1-C6 alkylsulfonyl group optionally substitutedwith at least one halogen atom; or a phenyl group,

R^(14az) is a hydrogen atom,

X¹⁸ is a nitrogen atom or CR^(18e)

(wherein R^(18e) is a hydrogen atom or a halogen atom), and

R^(18a), R^(18b), R^(18c) and R^(18d) are independently a hydrogen atomor a halogen atom.

“Aspect 3”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R^(4b) is a hydrogen atom,

R^(4c) is a hydrogen atom, a halogen atom, a cyano group, or a C1-C6alkyl group optionally substituted with at least one halogen atom,

R^(4d) is a hydrogen atom, a halogen atom, or a C1-C6 alkyl groupoptionally substituted with at least one halogen atom,

M is OR⁶

(wherein R⁶ is a C1-C6 alkyl group optionally substituted with at leastone halogen atom),

X^(a) is a nitrogen atom,

R^(14ay) is a hydrogen atom, a halogen atom, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom,

R^(14az) is a hydrogen atom,

X¹⁸ is a nitrogen atom,

R^(18a) is a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom, and

R^(18b), R^(18c) and R^(18d) are a hydrogen atom.

“Aspect 4”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R^(4b) is a hydrogen atom,

R^(4c) is a hydrogen atom, a halogen atom, a cyano group, or a C1-C6alkyl group optionally substituted with at least one halogen atom,

R^(4d) is a hydrogen atom, a halogen atom, or a C1-C6 alkyl groupoptionally substituted with at least one halogen atom,

M is OR⁶

(wherein R⁶ is a C1-C6 alkyl group optionally substituted with at leastone halogen atom),

X^(a) is CR^(14ax)

(wherein R^(14ax) is a hydrogen atom, a halogen atom, or a C1-C6 alkylgroup optionally substituted with at least one halogen atom),

R^(14ay) is a hydrogen atom, a halogen atom, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom,

R^(14az) is a hydrogen atom,

X¹⁸ is a nitrogen atom,

X^(18a) is a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom, and

R^(18b), R^(18c) and R^(18d) are a hydrogen atom.

“Aspect 5”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom or a methyl group,

R² is a hydrogen atom or a methyl group,

R³ is a hydrogen atom, a methyl group, or a methoxycarbonyl group,

R^(4a) is a hydrogen atom, a chlorine atom, a bromine atom, an iodineatom, a methyl group, an ethyl group, a trifluoromethyl group, a methoxygroup, or a phenyl group,

R^(4c) is a hydrogen atom, a fluorine atom, a chlorine atom, a bromineatom, an iodine atom, a methyl group, or a cyano group,

R^(4b) and R^(4d) are a hydrogen atom, a chlorine atom, or a methylgroup,

M is OR⁶

(wherein R⁶ is a methyl group),

X^(a) is a nitrogen atom,

R^(14ay) is a hydrogen atom, a chlorine atom, a bromine atom, a cyanogroup, a methyl group, an isopropyl group, a trifluoromethyl group, amethylthio group, a methylsulfinyl group, a methylsulfonyl group, or aphenyl group,

R^(14az) is a hydrogen atom or a bromine atom,

X¹⁸ is a nitrogen atom,

R^(18a) is a chlorine atom, and

R^(18b), R^(18c) and R^(18d) are a hydrogen atom.

“Aspect 6”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom or a methyl group,

R² is a hydrogen atom or a methyl group,

R³ is a hydrogen atom, a methyl group, or a methoxycarbonyl group

R^(4a) is a hydrogen atom, a chlorine atom, a bromine atom, an iodineatom, a methyl group, an ethyl group, a trifluoromethyl group, a methoxygroup, or a phenyl group,

R^(4c) is a hydrogen atom, a fluorine atom, a chlorine atom, a bromineatom, an iodine atom, a methyl group, or a cyano group,

R^(4b) and R^(4d) are a hydrogen atom, a chlorine atom, or a methylgroup,

M is OR⁶

(wherein R⁶ is a methyl group),

X^(a) is CR^(14ax)

(wherein R^(14ax) is a hydrogen atom or a halogen atom),

R^(14ay) is a hydrogen atom, a chlorine atom, a bromine atom, a cyanogroup, a methyl group, an isopropypl group, a trifluoromethyl group, amethylthio group, a methylsulfinyl group, a methylsulfonyl group, or aphenyl group,

R^(14az) is a hydrogen atom or a bromine atom,

X¹⁸ is a nitrogen atom,

R^(18a) is a chlorine atom, and

R^(18b), R^(18c) and R^(18d) are a hydrogen atom.

“Aspect 7”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a C1-C6 alkyl group optionally substituted with at least onehalogen atom.

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a hydrogen atom, a halogen atom, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom, a C1-C6 alkoxygroup optionally substituted with at least one halogen atom, or a phenylgroup optionally substituted with at least one halogen atom,

R^(4b), R^(4c) and R^(4d) are independently a hydrogen atom, a halogenatom, a cyano group, a C1-C6 alkyl group optionally substituted with atleast one halogen atom, or

R^(4b) and R^(4c) are bound to each other at their terminal ends to forma group: —CR⁴¹═CR⁴²—CR⁴³—═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ are a hydrogen atom),

M is OR⁶, SR⁷ or NR⁸R⁹

(wherein R⁶ and R⁷ are a C1-C6 alkyl group optionally substituted withat least one halogen atom, a C3-C6 alkoxyalkyl group optionallysubstituted with at least one halogen atom, a C2-C6 alkenyl groupoptionally substituted with at least one halogen atom, or a C3-C6alkynyl group optionally substituted with at least one halogen atom,

R⁸ and R⁹ are independently a hydrogen atom, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom, a C2-C6 alkenylgroup optionally substituted with at least one halogen atom, a C3-C6alkynyl group optionally substituted with at least one halogen atom,

or R⁸ and R⁹ are taken together with the nitrogen atom to which they arebound to form a pyrrolidin-1-yl group, a piperidino group, ahexamethyleneimin-1-yl group, a heptamethyleneimin-1-yl group, amorpholino group, a thiomorpholin-4-yl group, or a4-phenylpiperazin-1-yl group),

X^(a) is a nitrogen atom or CR^(14ax)

(wherein X^(14ax) is a hydrogen atom, a halogen atom, a cyano group, aC1-C6 alkyl group optionally substituted with at least one halogen atom,a C1-C6 alkylthio group optionally substituted with at least one halogenatom, or a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom),

R^(14ay) is a hydrogen atom, a halogen atom, a cyano group, a C1-C6alkyl group optionally substituted with at least one halogen atom, aC1-C6 alkylthio group optionally substituted with at least one halogenatom, or a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom, or a phenyl group,

R^(14az) is a hydrogen atom,

X¹⁸ is a nitrogen atom or a CR^(18e)

(wherein R^(18e) is a hydrogen atom or a halogen atom), and

R^(18a), R^(18b), R^(18c) and R^(18d) are independently a hydrogen atomor a halogen atom.

“Aspect 8”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen, or a C1-C6 alkyl group optionally substituted with atleast one halogen atom,

R³ is a hydrogen, a C1-C6 alkyl group optionally substituted with atleast one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a hydrogen atom, a halogen atom, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom, a C1-C6 alkoxygroup optionally substituted with at least one halogen atom, or a phenylgroup optionally substituted with at least one halogen atom.

R^(4b), R^(4c) and R^(4d) are independently a hydrogen atom, a halogenatom, a cyano group, a C1-C6 alkyl group optionally substituted with atleast one halogen atom, or

R^(4b) and R^(4c) are bound to each other at their terminal ends to forma group: —CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ are a hydrogen atom),

M is a hydrogen atom,

X^(a) is a nitrogen atom or CR^(14ax)

(wherein R^(14ax) is a hydrogen atom, a halogen atom, a cyano group, aC1-C6 alkyl group optionally substituted with at least one halogen atom,a C1-C6 alkoxy group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfony group optionallysubstituted with at least one halogen atom),

R^(14ay) is a hydrogen atom, a halogen atom, a cyano group, a C1-C6alkyl group optionally substituted with at least one halogen atom, aC1-C6 alkylthio group optionally substituted with at least one halogenatom, a C1-C6 alkylsulfinyl group optionally substituted with at leastone halogen atom, a C1-C6 alkylsulfonyl group optionally substitutedwith at least one halogen atom, or a phenyl group,

R^(14az) is a hydrogen atom,

X¹⁸ is a nitrogen atom or CR^(18e)

(wherein R^(18e) is a hydrogen atom or a halogen atom), and

R^(18a), R^(18b), R^(18c) and R^(18d) are independently a hydrogen atomor a halogen atom.

“Aspect 9”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R^(4b), R^(4c) and R^(4d) are independently a hydrogen atom, a halogenatom, a cyano group, or a C1-C6 alkyl group optionally substituted withat least one halogen atom,

or R^(4b) and R^(4c) are bound to each other at their terminal ends toform a group: —CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ are independently a hydrogen atom, ahalogen atom, a cyano group or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom),

M is R⁵, OR⁶, SR⁷ or NR⁸R⁹,

(wherein R⁵ is a hydrogen atom, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom,

R⁶ and R⁷ are a C1-C6 alkyl group optionally substituted with at leastone halogen atom, a C3-C6 alkoxyalkyl group optionally substituted withat least one halogen atom, a C2-C6 alkynyl group optionally substitutedwith at least one halogen atom or a C3-C6 alkynyl group optionallysubstituted with at least one halogen atom,

R⁸ and R⁹ are independently a hydrogen atom, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom, a C2-C6 alkenylgroup optionally substituted with at least one halogen atom, a C3-C6alkynyl group optionally substituted with at least one halogen atom,

or R⁸ and R⁹ are taken together with the nitrogen atom to which they arebound to form a pyrrolidin-1-yl group, a piperidino group, ahexamethyleneimin-1-yl group, a heptamethyleneimin-1-yl group, amorpholino group or a thiomorfolin-4-yl group),

X^(a) is a nitrogen atom or CR^(14ax)

(wherein R^(14ax) is a hydrogen atom, a halogen atom, a cyano group, aC1-C6 alkyl group optionally substituted with a halogen atom, a C1-C6alkoxy group optionally substituted with a halogen atom, a C1-C6alkylthio group optionally substituted with a halogen atom, a C1-C6alkylsulfinyl group optionally substituted with a halogen atom, or aC1-C6 alkylsulfonyl group optionally substituted with a halogen atom),

R^(14ay) and R^(14az) are independently a hydrogen atom, a halogen atom,a cyano group, a C1-C6 alkyl group optionally substituted with at leastone halogen atom, a C1-C6 alkoxy group optionally substituted with atleast one halogen atom, a C1-C6 alkylthio group optionally substitutedwith at least one halogen atom, a C1-C6 alkylsulfinyl group optionallysubstituted with at least one halogen atom, or a C1-C6 alkylsulfonylgroup optionally substituted with at least one halogen atom,

X¹⁸ is a nitrogen atom or CR^(18e),

(wherein R^(18e) is a hydrogen atom, a halogen atom, or C1-C6 alkylgroup optionally substituted with at least one halogen atom), and

R^(18a), R^(18b), R^(18c) and R^(18d) are independently a hydrogen atom,a halogen atom, or a C1-C6 alkyl group optionally substituted with atleast one halogen atom.

“Aspect 10”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R^(4b), R^(4c) and R^(4d) are independently a hydrogen atom, a halogenatom, a cyano group, or a C1-C6 alkyl group optionally substituted withat least one halogen atom,

or R^(4b) and R^(4c) are bound to each other at their terminal ends toform a group: —CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ are independently a hydrogen atom, ahalogen atom, a cyano group, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom),

M is R⁵, OR⁶, SR⁷ or NR⁸R⁹,

(wherein R⁵ is a hydrogen atom, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom,

R⁶ and R⁷ are a C1-C6 alkyl group optionally substituted with at leastone halogen atom, a C3-C6 alkoxyalkyl group optionally substituted withat least one halogen atom, a C2-C6 alkenyl group optionally substitutedwith at least one halogen atom, or a C3-C6 alkynyl group optionallysubstituted with at least one halogen atom,

R⁸ and R⁹ are independently a hydrogen atom, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom, a C2-C6 alkenylgroup optionally substituted with at least one halogen atom, a C3-C6alkynyl group optionally substituted with at least one halogen atom,

or R⁸ and R⁹ are taken together with a nitrogen atom to which they arebound to represent a pyrrolidin-1-yl group, a piperidino group, ahexamethyleneimin-1-yl group, a heptamethyleneimin-1-yl group, amorpholino or a thiomorpholin-4-yl group),

X^(a) is a nitrogen atom,

R^(14ay) and R^(14az) are independently a hydrogen atom, a halogen atom,a cyano group, a C1-C6 alkyl group optionally substituted with at leastone halogen atom, a C1-C6 alkoxy group optionally substituted with atleast one halogen atom, a C1-C6 alkylthio group optionally substitutedwith at least one halogen atom, a C1-C6 alkylsulfinyl group optionallysubstituted with at least one halogen atom, or a C1-C6 alkylsulfonylgroup optionally substituted with at least one halogen atom,

X¹⁸ is a nitrogen atom or CR^(18e),

(wherein R^(18e) is a hydrogen atom, a halogen atom, or a C1-C6 alkylgroup optionally substituted with at least one halogen atom), and

R^(18a), R^(18b), R^(18c) and R^(18d) are independently a hydrogen atom,a halogen atom or a C1-C6 alkyl group optionally substituted with atleast one halogen atom.

“Aspect 11”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R^(4b), R^(4c) and R^(4d) are independently a hydrogen atom, a halogenatom, a cyano group, or a C1-C6 alkyl group optionally substituted withat least one halogen atom,

or R^(4b) and R^(4c) are bound to each other at their terminal ends tofor a group: —CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ are independently a hydrogen atom, ahalogen atom, a cyano group, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom),

M is R⁵, OR⁶, SR⁷ or NR⁸R⁹,

(wherein R⁵ is a hydrogen atom, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom,

R⁶ and R⁷ are a C1-C6 alkyl group optionally substituted with at leastone halogen atom, a C3-C6 alkoxyalkyl group optionally substituted withat least one halogen atom, a C2-C6 alkenyl group optionally substitutedwith at least one halogen atom, or a C3-C6 alkynyl group optionallysubstituted with at least one halogen atom,

R⁸ and R⁹ are independently a hydrogen atom, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom, a C2-C6 alkenylgroup optionally substituted with at least one halogen atom, a C3-C6alkynyl group optionally substituted with at least one halogen atom,

or R⁸ and R⁹ are taken together with the nitrogen atom to which they arebound to form a pyrroridin-1-yl group, a piperidino group, ahexamethyleneimin-1-yl group, a heptamethyleneimin-1-yl group, amorpholino group or a thiomorpholin-4-yl group),

X^(a) is CR^(14ax)

(wherein R^(14ax) is a hydrogen atom, a halogen atom, a cyano group, aC1-C6 alkyl group optionally substituted with at least one halogen atom,a C1-C6 alkoxy group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom),

R^(14ay) and R^(14az) are independently a hydrogen atom, a halogen atom,a cyano group, a C1-C6 alkyl group optionally substituted with at leastone halogen atom, a C1-C6 alkoxy group optionally substituted with atleast one halogen atom, a C1-C6 alkylthio group optionally substitutedwith at least one halogen atom, a C1-C6 alkylsulfinyl group optionallysubstituted with at least one halogen atom, or a C1-C6 alkylsulfonylgroup optionally substituted with at least one halogen atom,

X¹⁸ is a nitrogen atom, or CR^(18e),

(wherein R^(18e) is a hydrogen atom, a halogen atom, or a C1-C6 alkylgroup optionally substituted with at least one halogen atom), and

R^(18a), R^(18b), R^(18c) and R^(18d) are independently a hydrogen atom,a halogen atom, or a C1-C6 alkyl group optionally substituted with atleast one halogen atom.

“Aspect 12”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R^(4b), R^(4c) and R^(4d) are independently a hydrogen atom, a halogenatom, a cyano group, or a C1-C6 alkyl group optionally substituted withat least one halogen atom,

or R^(4b) and R^(4c) are bound to each other at their terminal ends toform a group: —CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ are independently a hydrogen atom, ahalogen atom, a cyano group, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom),

M is R⁵, OR⁶, SR⁷ or NR⁸R⁹,

(wherein R⁵ is a hydrogen atom, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom,

R⁶ and R⁷ are a C1-C6 alkyl group optionally substituted with at leastone halogen atom, a C3-C6 alkoxyalkyl group optionally substituted withat least one halogen atom, a C2-C6 alkenyl group optionally substitutedwith at least one halogen atom, or a C3-C6 alkynyl group optionallysubstituted with at least one halogen atom,

R⁸ and R⁹ are independently a hydrogen atom, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom, a C2-C6 alkenylgroup optionally substituted with at least one halogen atom, a C3-C6alkynyl group optionally substituted with at least one halogen atom,

or R⁸ and R⁹ are taken together with the nitrogen atom to which they arebound to form a pyrroridin-1-yl group, a piperidino group, ahexamethyleneimin-1-yl group, a heptamethyleneimin-1-yl group, amorpholino group or a thiomorpholin-4-yl group),

X^(a) is CR^(14ax)

(wherein R^(14ax) is a hydrogen atom, a halogen atom, a cyano group, aC1-C6 alkyl group optionally substituted with at least one halogen atom,a C1-C6 alkoxy group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom),

R^(14ay) and R^(14az) are independently a hydrogen atom, a halogen atom,a cyano group, a C1-C6 alkyl group optionally substituted with at leastone halogen atom, a C1-C6 alkoxy group optionally substituted with atleast one halogen atom, a C1-C6 alkylthio group optionally substitutedwith at least one halogen atom, a C1-C6 alkylsulfinyl group optionallysubstituted with at least one halogen atom, or a C1-C6 alkylsulfonylgroup optionally substituted with at least one halogen atom,

X¹⁸ is a nitrogen atom, or CR^(18e),

(wherein R^(18e) is a halogen atom, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom), and

R^(18a), R^(18b), R^(18c) and R^(18d) are independently a hydrogen atom,a halogen atom, or a C1-C6 alkyl group optionally substituted with atleast one halogen atom.

“Aspect 13”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a hydrogen atom, a halogen atom, or a C1-C6 alkyl groupoptionally substituted with at least one halogen atom,

R^(4b) is a hydrogen atom,

R^(4c) is a hydrogen atom, a halogen atom, a cyano group, or a C1-C6alkyl group optionally substituted with at least one halogen atom,

R^(4d) is a hydrogen atom,

M is OR⁶,

R⁶ is a C1-C6 alkyl group optionally substituted with at least onehalogen atom,

X^(a) is a nitrogen atom,

R^(14ay) is a hydrogen atom, a halogen atom, or a C1-C6 alkyl groupoptionally substituted with at least one halogen atom,

R^(14az) is a hydrogen atom,

X¹⁸ is a nitrogen atom,

R^(18a) is a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom, and

R^(18b), R^(18c), R^(18d) are a hydrogen atom.

“Aspect 14”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a hydrogen atom, a halogen atom or a C1-C6 alkyl groupoptionally substituted with at least one halogen atom,

R^(4b) is a hydrogen atom,

R^(4c) is a hydrogen atom, a halogen atom, a cyano group, or a C1-C6alkyl group optionally substituted with at least one halogen atom,

R^(4d) is a hydrogen atom,

M is OR⁶,

R⁶ is a C1-C6 alkyl group optionally substituted with at least onehalogen atom,

X^(a) is a CR^(14ax)

(wherein R^(14ax) represents a hydrogen atom, a halogen atom, or a C1-C6alkyl group optionally substituted with at least one halogen atom),

R^(14ay) is a hydrogen atom, a halogen atom, or a C1-C6 alkyl groupoptionally substituted with at least one halogen atom,

R^(14az) is a hydrogen atom,

X¹⁸ is a nitrogen atom,

R^(18a) is a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom, and

R^(18b), R^(18c) and R^(18d) are a hydrogen atom.

“Aspect 15”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom or a methyl group,

R² is a hydrogen atom or a methyl group,

R³ is a hydrogen atom, a methyl group, or a methoxycarbonyl group,

R^(4a) is a chlorine atom, a bromine atom, an iodide atom, or a methylgroup,

R^(4c) is a chlorine atom, a bromine atom, an iodine atom, a methylgroup or a cyano group,

R^(4b) and R^(4d) are a hydrogen atom,

M is a OR⁶,

(wherein R⁶ is a methyl group),

X^(a) is a nitrogen atom,

R^(14ay) is a chlorine atom, a bromine atom, or a trifluoromethyl group,

R^(14az) is a hydrogen atom,

X¹⁸ is a nitrogen atom,

R^(18a) is a chlorine atom or a bromine atom, and

R^(18b), R^(18c) and R^(18d) are a hydrogen atom.

“Aspect 16”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom or a methyl group,

R² is a hydrogen atom or a methyl group,

R³ is a hydrogen atom, a methyl group, or a methoxycarbonyl group,

R^(4a) is a chlorine atom, a bromine atom, or an iodine atom, or amethyl group,

R^(4c) is a chlorine atom, a bromine atom, an iodine atom, a methylgroup or a cyano group,

R^(4b) and R^(4d) are a hydrogen atom,

M is OR⁶

(wherein R⁶ is a methyl group),

X^(a) is CR^(14ax)

(wherein R^(14ax) is a hydrogen atom, a chlorine atom or a bromineatom),

R^(14ay) is a chlorine atom, a bromine atom or a trifluoromethyl group,

R^(14az) is a hydrogen atom,

X¹⁸ is a nitrogen atom,

R^(18a) is a chlorine atom or a bromine atom, and

R^(18b), R^(18c) and R^(18d) are a hydrogen atom.

“Aspect 17”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a C1-C6 alkyl group optionally substituted with at least onehalogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R^(4b), R^(4c) and R^(4d) are independently a hydrogen atom, a halogenatom, a cyano group, or a C1-C6 alkyl group optionally substituted withat least one halogen atom,

or R^(4b) and R^(4c) are bound to each other at their terminal ends toform a group: —CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ are independently a hydrogen atom, ahalogen atom, a cyano group, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom),

M is OR⁶, SR⁷ or NR⁸R⁹,

(wherein R⁶ and R⁷ are a C1-C6 alkyl group optionally substituted withat least one halogen atom, a C3-C6 alkoxyalkyl group optionallysubstituted with at least one halogen atom, or a C2-C6 alkenyl groupoptionally substituted with at least one halogen atom, or a C3-C6alkynyl group optionally substituted with at least one halogen atom,

R⁸ and R⁹, each, independently, are a hydrogen atom, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom, a C2-C6 alkenylgroup optionally substituted with at least one halogen atom, a C3-C6alkynyl group optionally substituted with at least one halogen atom,

or R⁸ and R⁹ are taken together with the nitrogen atom to which they arebound to form a pyrrolidin-1-yl group, a piperidino group, ahexamethyleneimin-1-yl group, a heptamethyleneimin-1-yl group, amorpholino group, or a thiomorpholino-4-yl group),

X^(a) is a nitrogen atom or CR^(14ax)

(wherein R^(14ax) is a hydrogen atom, a halogen atom, a cyano group, aC1-C6 alkyl group optionally substituted with at least one halogen atom,a C1-C6 alkoxy group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom),

R^(14ay) and R^(14az) are independently a hydrogen atom, a halogen atom,a cyano group, a C1-C6 alkyl group optionally substituted with at leastone halogen atom, a C1-C6 alkoxy group optionally substituted with atleast one halogen atom, a C1-C6 alkylthio group optionally substitutedwith at least one halogen atom, a C1-C6 alkylsulfinyl group optionallysubstituted with at least one halogen atom, or a C1-C6 alkylsulfonylgroup optionally substituted with at least one halogen atom,

X¹⁸ is a nitrogen atom, or CR^(18e),

(wherein R^(18e) is a hydrogen atom, a halogen atom, or a C1-C6 alkylgroup optionally substituted with at least one halogen atom), and

R^(18a), R^(18b), R^(18c) and R^(18d) are independently a hydrogen atom,a halogen atom or a C1-C6 alkyl group optionally substituted with atleast one halogen atom.

“Aspect 18”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R^(4b), R^(4c) and R⁴ are independently a hydrogen atom, a halogen atom,a cyano group, or a C1-C6 alkyl group optionally substituted with atleast one halogen atom,

or R^(4b) and R^(4c) are bound at end to be —CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³, and R⁴⁴, each, independently, are a hydrogenatom, a halogen atom, a cyano group, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom,

M is a hydrogen atom,

X^(a) is a nitrogen atom or CR^(14ax)

(wherein R^(14ax) is a hydrogen atom, a halogen atom, a cyano group, aC1-C6 alkyl group optionally substituted with at least one halogen atom,a C1-C6 alkoxy group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom),

R^(14ay) and R^(14az), each, independently, are a hydrogen atom, ahalogen atom, a cyano group, a C1-C6 alkyl group optionally substitutedwith at least one halogen atom, a C1-C6 alkoxy group optionallysubstituted with at least one halogen atom, a C1-C6 alkylthio groupoptionally substituted with at least one halogen atom, a C1-C6alkylsulfinyl group optionally substituted with at least one halogenatom, or a C1-C6 alkylsulfonyl group optionally substituted with atleast one halogen atom,

X¹⁸ is a nitrogen atom or CR^(18e),

(wherein R^(18e) is a hydrogen atom, a halogen atom, or a C1-C6 alkylgroup optionally substituted with at least one halogen atom), and

R^(18a), R^(18b), R^(18c) and R^(18d) are independently a hydrogen atom,a halogen atom, or a C1-C6 alkyl group optionally substituted with atleast one halogen atom.

“Aspect 19”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a hydrogen atom, a halogen atom, a cyano group, or a nitrogroup or a C1-C6 alkyl group optionally substituted with at least onehalogen atom,

R^(4b) and R^(4c) are bound to each other at their terminal ends to forma group: —CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ are independently a hydrogen atom, ahalogen atom, a cyano group, a nitro group, or a C1-C6 alkyl groupoptionally substituted with at least one halogen atom),

R^(4d) is a hydrogen atom, a halogen atom, a cyano group, a nitro group,or a C1-C6 alkyl group optionally substituted with at least one halogenatom,

M is R⁵, OR⁶, SR⁷ or NR⁸R⁹,

(wherein R⁵ is a hydrogen atom, a C1-C6 alkyl group optionallysubstituted with at least one halogen atom, or a C3-C6 cycloalkyl group,

R⁶ and R⁷ are a C1-C6 alkyl group optionally substituted with at leastone halogen atom, a C3-C6 alkoxyalkyl group optionally substituted withat least one halogen atom, a C2-C6 alkenyl group optionally substitutedwith at least one halogen atom, or a C3-C6 alkynyl group optionallysubstituted with at least one halogen atom,

R⁸ and R⁹ are independently a hydrogen atom, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom, a C2-C6 alkenylgroup optionally substituted with at least one halogen atom, or a C3-C6alkynyl group optionally substituted with at least one halogen atom,

or R⁸ and R⁹ are taken together with the nitrogen atom to which they arebound to form a pyrroridin-1-yl group, a piperidino group, ahexamethyleneimin-1-yl group, a heptamethyleneimin-1-yl group, amorpholino group, a thiomorphorin-4-yl group, or a4-methylpiperazin-1-yl group),

X^(a) is a nitrogen atom or CR^(14ax)

R^(14ax), R^(14ay) and R^(14az) are independently a hydrogen atom, ahalogen atom, a cyano group, a C1-C6 alkyl group optionally substitutedwith at least one halogen atom, a C1-C6 alkoxy group optionallysubstituted with at least one halogen atom, a C1-C6 alkylthio groupoptionally substituted with at least one halogen atom, a C1-C6alkylsulfinyl group optionally substituted with at least one halogenatom, or a C1-C6 alkyl sulfonyl group optionally substituted with atleast one halogen atom,

X¹⁸ is a nitrogen atom, or a CR^(18e), and

R^(18a), R^(18b), R^(18c), R^(18d) and R^(18e) are independently ahydrogen atom, a halogen atom, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom.

“Aspect 20”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a hydrogen atom or a halogen atom,

R^(4b) and R^(4c) are bound to each other at their terminal ends to forma group: —CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ are independently a hydrogen atom, or ahalogen atom),

R^(4d) is a hydrogen atom,

M is R⁵, OR⁶, SR⁷ or NR⁸R⁹,

(wherein R⁵ is a hydrogen atom, a C1-C6 alkyl group optionallysubstituted with at least one halogen atom, or a C3-C6 cycloalkyl group,

R⁶ and R⁷ are a C1-C6 alkyl group optionally substituted with at leastone halogen atom, a C3-C6 alkoxyalkyl group optionally substituted withat least one halogen atom, a C2-C6 alkenyl group optionally substitutedwith at least one halogen atom, or a C3-C6 alkynyl group optionallysubstituted with at least one halogen atom,

R⁸ and R⁹ are independently a hydrogen atom, a C1-C6 alkyl groupoptionally substituted with at least one halogen atom, a C2-C6 alkenylgroup optionally substituted with at least one halogen atom, or a C3-C6alkynyl group optionally substituted with at least one halogen atom,

or R⁸ and R⁹ are taken together with the nitrogen atom to which they arebound to form a pyrroridin-1-yl group, a piperidino group, ahexamethyleneimin-1-yl group, a heptamethyleneimin-1-yl group, amorpholino group, a thiomorphorin-4-yl group, or a4-methylpiperazin-1-yl group),

X^(a) is a nitrogen atom or CR^(14ax),

R^(14ax), R^(14ay) and R^(14az) are independently a hydrogen atom, ahalogen atom, a cyano group, a C1-C6 alkyl group optionally substitutedwith at least one halogen atom, a C1-C6 alkoxy group optionallysubstituted with at least one halogen atom, a C1-C6 alkylthio groupoptionally substituted with at least one halogen atom, a C1-C6alkylsulfinyl group optionally substituted with at least one halogenatom, or a C1-C6 alkylsulfonyl group optionally substituted with atleast one halogen atom,

X¹⁸ is a nitrogen atom, or a CR^(18e), and

R^(18a), R^(18b), R^(18c), R^(18d) and R^(18e) are independently ahydrogen atom, a halogen atom, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom.

“Aspect 21”

A compound represented by the formula (1-2):

wherein,

R² represents a hydrogen atom or a C1-C6 alkyl group,

R³ represents a hydrogen atom or a methyl group,

R^(4a) represents a halogen atom or a methyl group,

R^(4c) represents a halogen atom,

R^(14ay) represents a halogen atom or a trifluoromethyl group,

X^(a) represents a nitrogen atom or CH,

R^(18a) represents a halogen atom, and

R¹⁰⁰ represents a C1-C6 alkyl group.

“Aspect 22”

A compound of the formula (1-2), wherein

R² is a C1-C6 alkyl group,

R³ is a hydrogen atom or a methyl group,

R^(4a) is a halogen atom, or a methyl group,

R^(4c) is a halogen atom,

R^(14ay) is a halogen atom or a trifluoromethyl group,

X^(a) is a nitrogen atom or CH, and

R^(18a) is a halogen atom.

“Aspect 23”

A compound represented by the formula (1-3):

wherein

R² represents a hydrogen atom or a C1-C6 alkyl group,

R³ represents a hydrogen atom or a methyl group,

R^(4a) represents a halogen atom or a methyl group,

R^(14ay) represents a halogen atom or a trifluoromethyl group,

X^(a) represents a nitrogen atom or CH,

R^(18a) represents a halogen atom, and

R¹⁰⁰ represents a C1-C6 alkyl group.

“Aspect 24”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R^(4b) is a hydrogen atom,

R^(4c) is a hydrogen atom, a halogen atom, a cyano group, or a C1-C6alkyl group optionally substituted with at least one halogen atom,

R^(4d) is a hydrogen atom,

M is OR⁶

(wherein R⁶ is a C1-C6 alkyl group optionally substituted with at leastone halogen atom, a C3-C6 alkoxyalkyl group optionally substituted withat least one halogen atom, a C2-C6 alkenyl group optionally substitutedwith at least one halogen atom, or a C3-C6 alkynyl group optionallysubstituted with at least one halogen atom),

X^(a) is a nitrogen atom or CR^(14ax)

(wherein R^(14ax) is a hydrogen atom, a halogen atom, a cyano group, aC1-C6 alkyl group optionally substituted with at least one halogen atom,a C1-C6 alkoxy group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom),

R^(14ay) is a hydrogen atom, a halogen atom, a cyano group, a C1-C6alkyl group optionally substituted with at least one halogen atom, aC1-C6 alkoxy group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom,

R^(14az) is a hydrogen atom,

X¹⁸ is a nitrogen atom

R^(18a) is a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom, and

R^(18b), R^(18c), R^(18d) are a hydrogen atom.

“Aspect 25”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R^(4b) is a hydrogen atom,

R^(4c) is a hydrogen atom, a halogen atom, a cyano group, or a C1-C6alkyl group optionally substituted with at least one halogen atom,

R^(4d) is a hydrogen atom,

M is OR⁶,

(wherein R⁶ is a C1-C6 alkyl group optionally substituted with at leastone halogen atom, a C3-C6 alkoxyalkyl group optionally substituted withat least one halogen atom, a C2-C6 alkenyl group optionally substitutedwith at least one halogen atom, or a C3-C6 alkynyl group optionallysubstituted with at least one halogen atom),

X^(a) is a nitrogen atom,

R^(14ay) is a hydrogen atom, a halogen atom, a cyano group, a C1-C6alkyl group optionally substituted with at least one halogen atom, aC1-C6 alkoxy group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom,

R^(14az) is a hydrogen atom,

X¹⁸ is a nitrogen atom,

R^(18a) is a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom, and

R^(18b), R^(18c), R^(18d) are a hydrogen atom.

“Aspect 26”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a halogen atom or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R^(4b) is a hydrogen atom,

R^(4c) is a hydrogen atom, a halogen atom, a cyano group, or a C1-C6alkyl group optionally substituted with at least one halogen atom,

R^(4d) is a hydrogen atom,

M is OR⁶,

(wherein R⁶ is a C1-C6 alkyl group optionally substituted with at leastone halogen atom, a C3-C6 alkoxyalkyl group optionally substituted withat least one halogen atom, a C2-C6 alkenyl group optionally substitutedwith at least one halogen atom, or a C3-C6 alkynyl group optionallysubstituted with at least one halogen atom),

X^(a) is a CR^(14ax)

(wherein R^(14ax) is a hydrogen atom, a halogen atom, a cyano group, aC1-C6 alkyl group optionally substituted with at least one halogen atom,a C1-C6 alkoxy group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom),

R^(14ay) is a hydrogen atom, a halogen atom, a cyano group, a C1-C6alkyl group optionally substituted with at least one halogen atom, aC1-C6 alkoxy group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom,

R^(14az) is a hydrogen atom,

X¹⁸ is a nitrogen atom,

R^(18a) is a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom, and

R^(18b), R^(18c) and R^(18d) are a hydrogen atom.

“Aspect 27”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a C1-C6 alkyl group optionally substituted with at least onehalogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R^(4b) is a hydrogen atom,

R^(4c) is a hydrogen atom, a halogen atom, a cyano group, or a C1-C6alkyl group optionally substituted with at least one halogen atom,

R^(4d) is a hydrogen atom,

M is OR⁶,

(wherein R⁶ is a C1-C6 alkyl group optionally substituted with at leastone halogen atom, a C3-C6 alkoxyalkyl group optionally substituted withat least one halogen atom, a C2-C6 alkenyl group optionally substitutedwith at least one halogen atom, or a C3-C6 alkynyl group optionallysubstituted with at least one halogen atom),

X^(a) is a nitrogen atom or CR^(14ax)

(wherein R^(14ax) is a hydrogen atom, a halogen atom, a cyano group, aC1-C6 alkyl group optionally substituted with at least one halogen atom,a C1-C6 alkoxy group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom),

R^(14ay) is a hydrogen atom, a halogen atom, a cyano group, a C1-C6alkyl group optionally substituted with at least one halogen atom, aC1-C6 alkoxy group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom,

R^(14az) is a hydrogen atom,

X¹⁸ is a nitrogen atom,

R^(18a) is a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom, and

R^(18b), R^(18c), R^(18d) are a hydrogen atom.

“Aspect 28”

A compound of the formula (1-1), wherein

R¹ is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R² is a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom,

R³ is a hydrogen atom, a C1-C6 alkyl group optionally substituted withat least one halogen atom, or a C2-C6 alkoxycarbonyl group,

R^(4a) is a halogen atom, a cyano group, a nitro group, or a C1-C6 alkylgroup optionally substituted with at least one halogen atom,

R^(4b) and R^(4c) are bound to each other at their terminal ends to forma group: —CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ are independently a hydrogen atom, ahalogen atom, a cyano group, a nitro group, or a C1-C6 alkyl groupoptionally substituted with at least one halogen atom),

R^(4d) is a hydrogen atom,

M is OR⁶,

(wherein R⁶ is a C1-C6 alkyl group optionally substituted with at leastone halogen atom, a C3-C6 alkoxyalkyl group optionally substituted withat least one halogen atom, a C2-C6 alkenyl group optionally substitutedwith at least one halogen atom, or a C3-C6 alkynyl group optionallysubstituted with at least one halogen atom),

X^(a) is a nitrogen atom or CR^(14ax)

(wherein R^(14ax) is a hydrogen atom, a halogen atom, a cyano group, aC1-C6 alkyl group optionally substituted with at least one halogen atom,a C1-C6 alkoxy group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom),

R^(14ay) is a hydrogen atom, a halogen atom, a cyano group, a C1-C6alkyl group optionally substituted with at least one halogen atom, aC1-C6 alkoxy group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom,

R^(14az) is a hydrogen atom,

X¹⁸ is a nitrogen atom,

R^(18a) is a halogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom, and

R^(18b), R^(18c), R^(18d) are a hydrogen atom.

“Aspect 29”

A compound represented by the formula (1-2), wherein

R² represents a hydrogen atom or a C1-C6 alkyl group,

R³ represents a hydrogen atom or a C1-C6 alkyl group,

R^(4a) represents a halogen atom or a methyl group,

R^(4c) represents a halogen atom,

R^(14ay) represents a halogen atom or a trifluoromethyl group,

X^(a) represents a nitrogen atom or CR^(14ax) (wherein R^(14ax) is ahydrogen atom or a halogen atom),

R^(18a) represents a halogen atom, and

R¹⁰⁰ represents a C1-C6 alkyl group.

“Aspect 30”

A compound of the formula (1-2), wherein

R² is a C1-C6 alkyl group,

R³ is a hydrogen atom or a C1-C6 alkyl group,

R^(4a) is a halogen atom, or a methyl group,

R^(4c) is a halogen atom,

R^(14ay) is a halogen atom or a trifluoromethyl group,

X^(a) is a nitrogen atom or CR^(14ax) (wherein R^(14ax) is a hydrogenatom or a halogen atom),

R^(18a) is a halogen atom, and

R¹⁰⁰ is a C1-C6 alkyl group.

“Aspect 31”

A compound of the formula (1-2), wherein

R² is a C1-C6 alkyl group,

R³ is a C1-C6 alkyl group,

R^(4a) is a halogen atom, or a methyl group,

R^(4c) is a halogen atom,

R^(14ay) is a halogen atom or a trifluoromethyl group,

X^(a) is a nitrogen atom or CR^(14ax) (wherein R^(14ax) represents ahydrogen atom or a halogen atom),

R^(18a) is a halogen atom, and

R¹⁰⁰ is a C1-C6 alkyl group.

“Aspect 32”

A compound represented by the formula (1-3), wherein

R² represents a hydrogen atom or a C1-C6 alkyl group,

R³ represents a hydrogen atom or a C1-C6 alkyl group,

R^(4a) represents a halogen atom or a methyl group,

R^(14ay) represents a halogen atom or a trifluoromethyl group,

X^(a) represents a nitrogen atom or CR^(14ax) (wherein R^(14ax)represents a hydrogen atom or a halogen atom),

R^(18a) represents a halogen atom, and

R¹⁰⁰ represents a C1-C6 alkyl group.

Hereinafter, a process for producing the present compound will beexplained.

The present compound can be produced, for example, by the followingProcess A-1 to Process C-1.

Process A-1

Among the present compounds, a compound represented by the formula(1-i):

wherein R¹, R², R³, R⁴, A¹, A², J and n are as defined above, Q′represents a group selected from the group consisting of Q1 to Q6(provided that the compound wherein Q′ is Q4, and R⁸ and R⁹ are ahydrogen atom is excluded) (hereinafter, referred to as the compound(1-i)) can be produced by reacting a compound represented by the formula(2):

wherein R¹, R², R³, R⁴, A¹, A², J and n are as defined above(hereinafter, referred to as the compound (2)), and a compoundrepresented by the formula (3):

L¹-Q′  (3)

wherein Q′ is as defined above, and L¹ represents a halogen atom or aQ′-O-group (provided that the case where Q′ is Q4, and R⁸ and R⁹ are ahydrogen atom is excluded) (hereinafter, referred to as the compound(3)).

The reaction is performed in the presence or the absence of a solvent.Examples of the solvent to be used in the reaction include ethers suchas 1,4-dioxane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether,and the like, halogenated hydrocarbons such as dichloromethane,chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, andthe like, hydrocarbons such as toluene, benzene, xylene, and the like,nitriles such as acetonitrile and the like, aprotic polar solvents suchas N,N-dimethylformamide, N-methlpyrrolidone,1,3-dimethyl-2-imidadzolidinone, dimethyl sulfoxide, and the like, and amixture thereof.

The amount of the compound (3) to be used in the reaction is usually 1to 2 mols per 1 mol of the compound (2).

The reaction is performed in the presence of a base, if necessary.Examples of the base include nitrogen-containing heterocyclic compoundssuch as pyridine, picoline, 2,6-lutidine,1,8-diazabicyclo[5,4,0]7-undecene (DBU), 1,5-diazabicyclo[4,3,0]5-nonene(DBN), and the like, tertiary amines such as triethylamine,N,N-diisopropylethylamine, and the like, and inorganic bases such aspotassium carbonate, sodium hydride, and the like. The amount of thebase when the reaction is performed in the presence of the base isusually 1 to 2 mols per 1 mol of the compound (2), while the base may beused in an excess amount in case that the base used is liquid under thereaction conditions such as pyridine, and the like.

The reaction temperature is usually in a range of 0 to 100° C., and thereaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the compound (1-i) can be isolated bypouring the reaction mixture into water and extracting the mixture withan organic solvent, or collecting a deposited precipitate by filtration.The isolated compound (1-i) may be further purified byrecrystallization, chromatography, or the like.

Process A-2

Among the present compounds, a compound represented by the formula(1-ii):

wherein R¹, R², R³, R⁴, A¹, A², A³⁴, J and n are as defined above, andR^(8a) represents a C1-C6 alkyl group optionally substituted with atleast one halogen atom; a C2-C6 alkoxyalkyl group optionally substitutedwith at least one halogen atom; a C2-C6 alkenyl group optionallysubstituted with at least one halogen atom; a C3-C6 alkynyl groupoptionally substituted with at least one halogen atom; a C3-C6cycloalkyl group optionally substituted with one or more independentsubstituents selected from the group consisting of (1) a halogen atomand (2) a C1-C6 alkyl group; a phenyl group optionally substituted witha 1 to 5 independent substituents selected from the group consisting of(1) a halogen atom (2) a cyano group, (3) a nitro group, (4) a C1-C6alkyl group optionally substituted with at least one halogen atom, (5) aC1-C6 alkoxy group optionally substituted with at least one halogenatom, (6) a C1-C6 alkylthio group optionally substituted with at leastone halogen atom, (7) a C1-C6 alkylsulfinyl group optionally substitutedwith at least one halogen atom, (8) a C1-C6 alkylsulfonyl groupoptionally substituted with at least one halogen atom, (9) a C2-C6dialkylamino group optionally substituted with at least one halogen atomand (10) a C2-C6 alkoxycarbonyl group optionally substituted with atleast one halogen atom; a 5- to 6-membered heteroaryl group optionallysubstituted with 1 to 5 independent substituents selected from the groupconsisting of (1) a halogen atom, (2) a cyano group, (3) a nitro group,(4) a C1-C6 alkyl group optionally substituted with at least one halogenatom and (5) a C1-C6 alkoxy group optionally substituted with at leastone halogen atom; or a C7-C9 phenylalkyl group whose benzene ring moietymay be substituted with 1 to 5 independent substituents selected fromthe group consisting of (1) a halogen atom, (2) a cyano group, (3) anitro group, (4) a C1-C6 alkyl group optionally substituted with atleast one halogen atom and (5) a C1-C6 alkoxy group optionallysubstituted with at least one halogen atom (hereinafter, referred to asthe compound (1-ii)) can be produced by reacting the compound (2) with acompound represented by the formula (4):

A³⁴=C═N—R^(8a)  (4)

wherein A³⁴ and R^(8a) are as defined above (hereinafter, referred to asthe compound (4)).

The reaction is performed in the presence or the absence of a solvent.Examples of the solvent to be used in the reaction include ethers suchas 1,4-dioxane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether,and the like, halogenated hydrocarbons such as dichloromethane,chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, andthe like, hydrocarbons such as toluene, benzene, xylene, and the like,nitriles such as acetonitrile, and the like, aprotic polar solvents suchas N,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and the like, and amixture thereof.

The amount of the compound (4) used in the reaction is usually 1 to 2mols per 1 mol of the compound (2).

The reaction temperature is usually in a range of 0 to 100° C., and thereaction time is a usually a range of 0.1 to 24 hours.

After completion of the reaction, the compound (1-ii) can be isolated bypouring the reaction mixture into water, and extracting the mixture withan organic solvent, or collecting a deposited precipitate by filtration.The isolated compound (1-ii) may be further purified byrecrystallization, chromatography, or the like.

Process A-3

Among the present compounds, a compound represented by the formula(1-iii):

wherein R¹, R², R³, R⁴, A¹, A², A³⁴, J and n are as defined above(hereinafter, referred to as the compound (I-iii)) can be produced byreacting the compound (2) and a cyanate or a thiocyanate.

The reaction is performed in the presence of a solvent. Examples of thesolvent used in the reaction include acids such as organic acids such asacetic acids, and the like and mineral acids such as hydrochloric acid,and the like, as well as a mixture of these acids and water, chloroform,or the like.

The amount of the cyanate or the thiocyanate used in the reaction isusually 1 to 2 mols per 1 mol of the compound (2).

The reaction temperature is usually in a range of 0 to 100° C., and thereaction time is usually in a range of 0.1 to 24 hours.

Examples of the cyanate or the thiocyanate include potassium cyanate,sodium cyanate, ammonium cyanate, potassium thiocyanate, sodiumthiocyanate and ammonium thiocyanate.

After completion of the reaction, the compound (I-iii) can be isolatedby pouring the reaction mixture into water and extracting the mixturewith an organic solvent, or collecting a deposited precipitate byfiltration. The isolated Compound (I-iii) may be further purified byrecrystallization, chromatography, or the like.

Process B-1

The present compound can be produced by reacting a compound representedby the formula (6):

wherein R¹, R², R³, R⁴, A², Q and n are as defined above (hereinafter,referred to as Compound (6)) and a compound represented by the formula(7):

wherein A¹ and J are as define above, and L² represents a halogen atom(hereinafter, referred to as the compound (7)).

The reaction is performed in the presence or the absence of a solvent.Examples of the solvent used in the reaction include ethers such as1,4-dioxane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether,and the like, halogenated hydrocarbons such as dichloromethane,chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, andthe like, hydrocarbons such as toluene, benzene, xylene, and the like,nitriles such as acetonitrile, and the like, aprotic polar solvents suchas N,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and the like, and amixture thereof.

The amount of the compound (7) used in the reaction is usually 1 to 2mols per 1 mol of the compound (6).

The reaction is performed in the presence of a base, if necessary.Examples of the base include nitrogen-containing heterocyclic compoundssuch as pyridine, picoline, 2,6-lutidine,1,8-diazabicyclo[5,4,0]7-undecene (DBU), 1,5-diazadicyclo[4,3,0]5-nonene(DBN), and the like, tertiary amines such as triethylamine,N,N-diisopropylethylamine, and the like, and inorganic bases such aspotassium carbonate, sodium hydride, and the like. The amount of thebase when the reaction is performed in the presence of the base isusually 1 to 2 mole per 1 mol of the compound (6), while the base may beused in an excess amount in case that the base used is liquid under thereaction conditions such as pyridine, and the like.

The reaction temperature is usually in a range of 0 to 100° C., and thereaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the present compound can be isolatedby pouring the reaction mixture into water, and extracting the mixturewith an organic solvent, or collecting a deposited precipitation byfiltration. The isolated present compound may be further purified byrecrystallization, chromatography, or the like.

Process B-2

Among the present compounds, a compound represented by the formula(I-iv):

wherein R¹, R², R³, R⁴, A², J, Q and n are as defined above (hereinafterreferred to as the compound (I-iv)) can be produced by reacting thecompound (6) and a compound represented by the formula (8):

wherein J is as defined above (hereinafter, referred to as the compound(8)) in the presence of a dehydrating agent.

The reaction is performed in the presence or the absence of a solvent.Examples of the solvent to be used in the reaction include ethers suchas 1,4-dioxane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether,and the like, halogenated hydrocarbons such as dichloromethane,chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, andthe like, hydrocarbons such as toluene, benzene, xylene, and the like,nitriles such as acetonitrile, and the like, aprotic polar solvents suchas N,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and the like, and amixture thereof.

The amount of the compound (8) used in the reaction is usually 1 to 2mols per 1 mol of the compound (6).

Examples of the dehydrating agent to be used in the reaction includecarbodiimides such as dicyclohexylcarbodiimide (DCC),1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (WSC), andthe like. The amount of the dehydrating agent to be used is usually 1 to2 mols per 1 mol of the compound (6).

The reaction temperature is usually in a range of 0 to 100° C., and thereaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the compound (I-iv) can be isolated bypouring the reaction mixture into water, and extracting the mixture withan organic solvent, or collecting a deposited precipitate by filtration.The isolated compound (1-iv) may be further purified byrecrystallization, chromatography, or the like.

Process C-1

Among the present compounds, a compound represented by the formula(1-v):

wherein R², R³, R⁴, J, Q and n are as defined above (hereinafter,referred to as the compound (1-v)) can be produced by reacting acompound represented by the formula (9):

wherein R⁴, J and n are as defined above (hereinafter, referred to asthe compound (9)) and a compound represented by the formula (10):

wherein R², R³ and Q are as defined above (hereinafter, referred to asthe compound (10)).

The reaction is performed in the presence or the absence of a solvent.Examples of the solvent used in the reaction include ethers such as1,4-dioxane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether,and the like, halogenated hydrocarbons such as dichloromethane,chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, andthe like, hydrocarbons such as toluene, benzene, xylene, and the like,nitriles such as acetonitrile, and the like, aprotic polar solvents suchas N,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidaozolidinone, dimethyl sulfoxide, and the like, and amixture thereof.

The amount of the compound (10) to be used in the reaction is usually 1to 20 mols per 1 mol of the compound (9).

The reaction temperature is usually in a range of 0 to 100° C., and thereaction time is usually in a range of 0.1 to 48 hours.

After completion of the reaction, the compound (1-v) can be isolated bypouring the reaction mixture into water, and extracting the mixture withan organic solvent, or collecting a deposited precipitate by filtration.The isolated compound (1-v) may be further purified byrecrystallization, chromatography, or the like.

Process C-2

Among the present compounds, a compound represented by the formula(1-vi):

wherein R², R³, R⁴, A¹, J, Q and n are as defined above, R^(1-a)represents a C1-C6 alkyl group optionally substituted with at least onehalogen atom; a C2-C6 cyanoalkyl group; a C2-C6 alkoxyalkyl groupoptionally substituted with at least one halogen atom; a C2-C6 alkenylgroup optionally substituted with at least one halogen atom; a C3-C6alkynyl group optionally substituted with at least one halogen atom; ora C7-C9 phenylalkyl group in which a benzene ring part may besubstituted with 1 to 5 independent substituents selected from the groupconsisting of (1) a halogen atom, (2) a cyano group, (3) a nitro group,(4) a C1-C6 alkyl group optionally substituted with at least one halogenatom and (5) a C1-C6 alkoxy group optionally substituted with at leastone halogen atom (hereinafter, referred to as the compound (1-vi)) canbe produced by reacting a compound represented by the formula (11):

wherein R^(1-a), R⁴, A¹, J and n are as defined above, and L³ representsa halogen atom (hereinafter, referred to as the compound (11)) and thecompound (10).

The reaction is performed in the presence or the absence of a solvent.Examples of the solvent to be used in the reaction include ethers suchas 1,4-dioxane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether,and the like, halogenated hydrocarbons such as dichloromethane,chloroform, carbon tetrachloride, 1,2-dichlorethane, chlorobenzene, andthe like, hydrocarbons such as toluene, benzene, xylene, and the like,nitriles such as acetonitrile, and the like, aprotic polar solvents suchas N,N-diethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and the like, and amixture thereof.

The amount of the compound (10) to be used in the reaction is usually 1to 2 mols per 1 mol of the compound (11).

The reaction is performed in the presence of a base, if necessary.Examples of the base include nitrogen-containing heterocyclic compoundssuch as pyridine, picoline, 2,6-lutidine,1,8-diazabicyclo[5,4,0]7-undecene (DBU), 1,5-diazabicyclo[4,3,0]5-nonene(DBN), and the like, tertiary amines such as triethylamine,N,N-diisopropylethylamine, and the like, and inorganic bases such aspotassium carbonate, sodium hydride, and the like. The amount of thebase to be used when the reaction is performed in the presence of thebase is usually 1 to 2 mols per 1 mol of the compound (11), while thebase may be used in an excess amount in the case that the base used isliquid under the reaction conditions such as pyridine and the like.

The reaction temperature is usually in a range of 0 to 100° C., and thereaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the compound (1-vi) can be isolatedafter pouring the reaction mixture into water, and extracting themixture with an organic solvent, or collecting a deposited precipitateby filtration. The isolated compound (1-vi) may be further purified byrecrystallization, chromatography or the like.

Process C-3

The compound (1-vi) can also be produced by reacting a compoundrepresented by the formula (12):

wherein R⁴, R^(1-a), A¹, J and n are as defined above (hereinafter,referred to as Compound (12)) and the compound (10) in the presence of adehydrating agent.

The reaction is performed in the presence or the absence of a solvent.Examples of the solvent to be used in the reaction include ethers suchas 1,4-dioxane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether,and the like, halogenated hydrocarbons such as dichloromethane,chloroform, carbon tetrachloride, 1,2-dichlroethane, chlorobenzene, andthe like, hydrocarbons such as toluene, benzene, xylene, and the like,nitriles such as acetonitrile, and the like, aprotic polar solvents suchas N,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and the like, and amixture thereof.

The amount of the compound (10) used in the reaction is usually 1 to 2mols per 1 mol of the compound (12).

Examples of the dehydrating agent used in the reaction includecarbodiimides such as dicyclohexylcarbodiimide (DCC),1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (WSC), andthe like. The amount of the dehydrating agent to be used is usually 1 to2 mols per 1 mol of the compound (12).

The reaction temperature is usually in a range of 0 to 100° C., and thereaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the compound (1-vi) can be isolated bypouring the reaction mixture into water and extracting the mixture withan organic solvent, or collecting a deposited precipitate by filtration.The isolated compound (1-vi) may be further purified byrecrystallization, chromatography, or the like.

Then, a process for producing intermediates for producing the presentcompound will be explained.

Reference Process 1

Among the compound (2), a compound represented by the formula (2-i):

wherein R², R³, R⁴, J and n are as defined above (hereinafter, referredto as the compound (2-i)) can be produced by reacting the compound (9)and a compound represented by the formula (13):

wherein R² and R³ are as defined above (hereinafter, referred to as thecompound (13)).

The reaction is performed in the presence or the absence of a solvent.Examples of the solvent used in the reaction include ethers such as1,4-dioxane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether,and the like, halogenated hydrocarbons such as dichloromethane,chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene andthe like, hydrocarbons such as toluene, benzene, xylene and the like,nitriles such as acetonitrile, and the like, aprotic polar solvents suchas N,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and the like,alcohols such as methanol, ethanol, 2-propanol, and the like, and amixture thereof.

The amount of the compound (13) to be used in the reaction is usually 1to 5 mols per 1 mol of the compound (9).

The reaction temperature is usually in a range of −50 to 100° C., andthe reaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the compound (2-i) can be isolated bypouring the reaction mixture into water, and extracting the mixture withan organic solvent, or collecting a deposited precipitate by filtration.The isolated compound (2-i) may be further purified byrecrystallization, chromatography, or the like.

Reference Process 2

Among the compound (2), a compound represented by the formula (2-ii):

wherein R², R³, R⁴, J and n are as defined above (hereinafter, referredto as Compound (2-ii)) can be produced by reacting a compoundrepresented by the formula (14):

wherein R⁴, J and n are as defined above (hereinafter, referred to asthe compound (14)) and the compound (13).

The reaction is performed in the presence or the absence of a solvent.Examples of the solvent to be used in the reaction include ethers suchas 1,4-dioxane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether,and the like, halogenated hydrocarbons such as dichloromethane,chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene andthe like, hydrocarbons such as toluene, benzene, xylene, and the like,nitriles such as acetonitrile, and the like, aprotic polar solvents suchas N,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and the like,alcohols such as methanol, ethanol, 2-propanol, and the like, and amixture thereof.

The amount of the compound (13) to be used in the reaction is usually 1to 5 mols per 1 mol of the compound (14).

The reaction temperature is usually in a range of −50 to 100° C., andthe reaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the compound (2-ii) can be isolated bypouring the reaction mixture into water, and extracting the mixture withan organic solvent, or collecting a deposited precipitate by filtration.The isolated compound (2-ii) may be further purified byrecrystallization, chromatography, or the like.

Reference Process 3

Among the compound (2), a compound represented by the formula (2-iii):

wherein R^(1-a), R², R³, R⁴, A¹, J and n are as defined above(hereinafter, referred to as the compound (2-iii)) can be produced byreacting the compound (11) and the compound (13).

The reaction is performed in the presence or the absence of a solvent.Examples of the solvent used in the reaction include ethers such as1,4-dioxane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether,and the like, halogenated hydrocarbons such as dichloromethane,chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, andthe like, hydrocarbons such as toluene, benzene, xylene, and the like,nitriles such as acetonitrile, and the like, aprotic polar solvents suchas N,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and the like, and amixture thereof.

The amount of Compound (13) used in the reaction is usually 2 to 10 molsper 1 mol of the compound (11).

The reaction temperature is usually in a range of −50 to 100° C., andthe reaction time is in a range of 0.1 to 24 hours.

After completion of the reaction, the compound (2-iii) can be isolatedby pouring the reaction mixture into water, and extracting the mixturewith an organic solvent, or collecting a deposited precipitate byfiltration. The isolated compound (2-iii) may be further purified byrecrystallization, chromatography, or the like.

Reference Process 4

The compound (9) can be produced by reacting a compound represented bythe formula (16).

wherein R⁴ and n are as defined above (hereinafter, referred to as thecompound (16)) and a compound represented by the formula (7′):

wherein J and L² are as defined above (hereinafter, referred to asCompound (7′)).

The reaction is performed in the presence or the absence of a solvent inthe presence of a base. Examples of the solvent to be used in thereaction include ethers such as 1,4-dioxane, diethyl ether,tetrahydrofuran, methyl tert-butyl ether, and the like, halogenatedhydrocarbons such as dichloromethane, chloroform, carbon tetrachloride,1,2-dichloroethane, chlorobenzene, and the like, hydrocarbons such astoluene, benzene, xylene, and the like, nitriles such as acetonitrile,and the like, aprotic polar solvents such as N,N-dimethylformamide,N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide,and the like, and a mixture thereof.

The amount of the compound (7′) used in the reaction is usually 0.5 to 2mols per 1 mol of the compound (16).

Examples of the base to be used in the reaction includenitrogen-containing heterocyclic compounds such as pyridine, picoline,2,6-lutidine, 1,8-diazabicyclo[5,4,0]7-undecene(DBU),1,5-diazabicyclo[4,3,0]5-nonene (DBN), and the like, tertiary aminessuch as triethylamine, N,N-diisopropylethylamine, and the like, andinorganic bases such as potassium carbonate, sodium hydride, and thelike. The amount of the base to be used is usually 1 to 2 mols per 1 molof the compound (16), while the base may be used in an excess amount incase that the base is liquid under the reaction conditions such aspyridine, and the like.

The reaction temperature is usually in a range of 50 to 150° C., and thereaction time is usually in a range of 1 to 24 hours.

After completion of the reaction, the compound (9) can be isolated bypouring the reaction mixture into water, and extracting the mixture withan organic solvent, or collecting a deposited precipitates byfiltration. The isolated compound (9) may be further purified byrecrystallization, chromatography, or the like.

Reference Process 5

The compound (9) can be produced by reacting a compound represented bythe formula (17):

wherein R⁴ and n are as defined above (hereinafter, referred to asCompound (17)) and the compound (7′).

The reaction is performed in the presence or the absence of a solvent.Examples of the solvent to be used in the reaction include ethers suchas 1,4-dioxane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether,and the like, halogenated hydrocarbons such as dichloromethane,chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, andthe like, hydrocarbons such as toluene, benzene, xylene, and the like,nitriles such as acetonitrile, and the like, aprotic polar solvents suchas N,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and the like, and amixture thereof.

The process comprises the following step 5-1 and step 5-2.

Step 5-1

This step is performed by reacting the compound (17) and the compound(7′) in the presence of a base.

The amount of the compound (7′) to be used in this step is usually 1 to2 mols per 1 mol of the compound (17). Examples of the base includenitrogen-containing heterocyclic compounds such as pyridine, picoline,2,6-lutidine, 1,8-diazabicyclo[5,4,0]7-undecene (DBU),1,5-diazabicyclo[4,3,0]5-nonene (DBN), and the like, tertiary aminessuch as triethylamine, N,N-diisopropylethylamine, and the like, andinorganic bases such as potassium carbonate, sodium hydride, and thelike. The amount of the base to be used is usually 1 to 2 mols per 1 molof the compound (17).

The reaction temperature of this step is usually in a range of 0 to 50°C., and the reaction time is usually in a range of 0.1 to 24 hours.

After completion of this step, usually, the reaction mixture is used asit is in the next step 5-2.

Step 5-2

This step is performed by reacting the reaction mixture in the step 5-1and a sulfonyl halide in the presence of a base.

Examples of the sulfonyl halide used in this step includemethanesulfonyl chloride, p-toluenesulfonyl chloride, andtrifluoromethanesulfonyl chloride. The amount of the sulfonyl halide tobe used in this step is usually 1 to 2 mols per 1 mol of the compound(17) used in the step 5-1.

Examples of the base include the same bases as those described withrespect to the step 5-1. The amount of the base is usually 2 to 4 molsper 1 mol of the compound (17) used in the step 5-1.

The reaction temperature of this step is usually in a range of 0 to 50°C., and the reaction time is usually in a range of 0.1 to 24 hours.

After completion of this step, the compound (9) can be isolated bypouring the reaction mixture into water, followed by conventionalextraction with an organic solvent. The isolated compound (9) may befurther purified by recrystallization, chromatography, or the like.

Reference Process 6

The compound (14) can be produced by reacting the compound (9) with athiocarbonylation agent.

The reaction is performed in the presence or the absence of a solvent.Examples of the solvent to be used in the reaction include ethers suchas 1,4-dioxane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether,diglyme, and the like, halogenated hydrocarbons such as dichloromethane,chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, andthe like, hydrocarbons such as toluene, benzene, xylene, and the like,nitriles such as acetonitrile, and the like, pyridines such as pyridine,picoline, lutidine, and the like, and a mixture thereof.

Examples of the thiocarbonylation agent to be used in the reactioninclude diphosphorus pentasulfide, a Lawesson's reagent(2,4-bis-(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane 2,4-disulfide),and the like.

The amount of the thiocarbonylation agent to be used in the reaction isusually 1 to 3 mols per 1 mol of the compound (9).

The reaction temperature is usually in a range of 0° C. to 200° C., andthe reaction time is usually in a range of 1 to 24 hours.

After completion of the reaction, the compound (14) can be isolated bycollecting a precipitate deposited in the reaction mixture byfiltration, or extracting the reaction mixture with an organic solvent.The isolated compound (14) may be further purified by recrystallization,chromatography, or the like.

Reference Process 7

The compound (11) can be produced by reacting the compound (12) with ahalogenating agent.

The reaction is performed in the presence or the absence of a solvent.Examples of the solvent to be used in the reaction include ethers suchas 1,4-dioxane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether,and the like, halogenated hydrocarbons such as dichloromethane,chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, andthe like, hydrocarbons such as toluene, benzene, xylene, and the like,nitriles such as acetonitrile, and the like, aprotic polar solvents suchas N,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and the like, and amixture thereof.

Examples of the halogenating agent to be used in the reaction includethionyl chloride, thionyl bromide, phosphorus oxychloride, phosphorusoxybromide, phosphorus pentachloride, oxalyl chloride, and phosgene.

The amount of the halogenating agent to be used in the reaction isusually 1 to 2 mols per 1 mol of the compound (12) and, in some cases,the halogenating agent may be used in an excess amount.

The reaction temperature is usually in a range of 0° C. to 150° C., andthe reaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the compound (11) can be isolated bycollecting a precipitate deposited in the reaction mixture, orconcentrating the reaction mixture. The isolated compound (11) isusually used as it is in the next step and, if necessary, may be furtherpurified by recrystallization, or the like.

Reference Process 8

The compound (12) can be produced by reacting a compound represented bythe formula (18′):

wherein R^(1-a), R⁴ and n are as defined above (hereinafter, referred toas the compound (18′)) and the compound (7).

The reaction is performed in the presence or the absence of a solvent.Examples of the solvent used in the reaction include ethers such as1,4-dioxane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether,and the like, halogenated hydrocarbons such as dichloromethane,chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, andthe like, hydrocarbons such as toluene, benzene, xylene, and the like,nitriles such as acetonitrile, and the like, aprotic polar solvents suchas N,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and the like, and amixture thereof.

The amount of the compound (7) to be used in the reaction is usually 1to 2 mols per 1 mol of the compound (18′).

The reaction is performed in the presence of a base. Examples of thebase to be used include nitrogen-containing heterocyclic compounds suchas pyridine, picoline, 2,6-lutidine, 1,8-diazabicyclo[5,4,0]7-undecene(DBU), 1,5-diazabicyclo[4,3,0]5-nonene (DBN), and the like, tertiaryamines such as triethylamine, N,N-diisopropylethylamine, and the like,inorganic bases such as potassium carbonate, sodium hydride, and thelike. The amount of the base to be used is usually 1 to 2 mols per 1 molof the compound (18′).

The reaction temperature is usually in a range of 0 to 50° C., and thereaction time is usually in range of 0.1 to 24 hours.

After completion of the reaction, the compound (12) can be isolated bypouring the reaction mixture into water, followed by conventionalextraction with an organic solvent, or collecting a depositedprecipitate by filtration. The isolated compound (12) may be furtherpurified by recrystallization, chromatography, or the like.

Reference Process 9

The compound (6) can be produced by reacting a compound represented bythe formula (20):

wherein R¹, R⁴ and n are as defined above (hereinafter, referred to asthe compound 20)) and the compound (10).

The reaction is performed in the presence or the absence of a solvent.Examples of the solvent used in the reaction include ethers such as1,4-dioxane, diethyl ether, tetrahydrofuran, methyl tert-butyl ether,and the like, halogenated hydrocarbons such as dichloromethane,chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, andthe like, hydrocarbons such as toluene, benzene, xylene, and the like,nitriles such as acetonitrile, and the like, aprotic polar solvents suchas N,N-dimethylformamide, N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and the like,alcohols such as methanol, ethanol, isopropyl alcohol, and the like, anda mixture thereof.

The amount of the compound (10) to be used in the reaction is usually 1to 2 mols per 1 mol of the compound (20).

The reaction temperature is usually in a range of −20 to 150° C., andthe reaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the compound (20) can be isolated bypouring the reaction mixture into water, and extracting the mixture withan organic solvent, or collecting a deposited precipitate by filtration.The isolated Compound (20) may be further purified by recrystallization,chromatography, or the like.

The compounds (3), (4) and (13) are known compounds, or can be producedfrom known compounds according to known processes (e.g. see OrganicFunctional Group Preparations, 2nd edition, Vol. 1, chapter 12, p.359-376 (Stanley R. Sandler, Wolf Karo.) or Organic Functional GroupPreparations, 2nd edition, Vol. 1, chapter 14, p. 434-465 (Stanley R.Sandler, Wolf Karo.)).

As an aspect of the compound (2), the following compound is mentioned:

A hydrazide compound of the formula (II):

wherein

R^(1-i) represents a hydrogen atom, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom,

R^(2-i) represents a hydrogen atom, or a methyl group,

R^(4a) represents a halogen atom, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom,

R^(4b), R^(4c) and R^(4d) independently represent a hydrogen atom, ahalogen atom, a cyano group, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom,

or R^(4b) and R^(4c) are bound to each other at their terminal ends toform a group T1: —CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴—

(wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ independently represent a hydrogen atom,a halogen atom, a cyano group, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom),

X^(a) represents a nitrogen atom or CR^(14ax) (wherein R^(14ax)represents a hydrogen atom, a halogen atom, a cyano group, a C1-C6 alkylgroup optionally substituted with at least one halogen atom, a C1-C6alkoxy group optionally substituted with at least one halogen atom, aC1-C6 alkylthio group optionally substituted with at least one halogenatom, a C1-C6 alkylsulfinyl group optionally substituted with at leastone halogen atom, or a C1-C6 alkylsulfonyl group optionally substitutedwith at least one halogen atom),

R^(14ay) and R^(14az) independently represent a hydrogen atom, a halogenatom, a cyano group, a C1-C6 alkyl group optionally substituted with atleast one halogen atom, a C1-C6 alkoxy group optionally substituted withat least one halogen atom, a C1-C6 alkylthio group optionallysubstituted with at least one halogen atom, a C1-C6 alkylsulfinyl groupoptionally substituted with at least one halogen atom, or a C1-C6alkylsulfonyl group optionally substituted with at least one halogenatom,

X¹⁸ represents a nitrogen atom or CR^(18e) (wherein R^(18e) represents ahydrogen atom, a halogen atom, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom),

R^(18a) represents a halogen atom, or a C1-C6 alkyl group optionallysubstituted with at least one halogen atom, and

R^(18b), R^(18c) and R^(18d) independently represent a hydrogen atom, ahalogen atom, or a C1-C6 alkyl group optionally substituted with atleast one halogen atom.

The compound (10) can be produced, for example, according to thefollowing scheme (1).

In Scheme (I), A³⁴, L¹, Q′, R², R³ and R^(8a) are as defined above.

Among the compound (10), a compound represented by the formula (10-i):

wherein R², R³ and R⁶ are as defined above, can be produced, forexample, according to the following scheme (2).

In Scheme (2), R², R³ and R⁶ are as defined above.

The compound (17) can be produced, for example, according to thefollowing Scheme (3).

In Scheme (3), R⁴ and n are as defined above.

The compounds (16), (18′) and (20) can be produced, for example,according to the following Scheme (4).

In Scheme (4), R^(1-a), R⁴ and n are as defined above, and L⁴ representsa leaving group (e.g. a halogen atom, a methanesulfonyloxy group, ap-toluenesulfonyloxy group etc.).

Among the compounds (17) and (18), a compound represented by the formula(17-i):

wherein R¹ and R⁴ are as defined above, R^(4c-x) represents a halogenatom or a cyano group, and n−1 represents an integer of 0 to 3, can beproduced, for example, according to the following Scheme (5).

In Scheme (5), R¹, R⁴ and n−1 are as defined above, and halo representsa halogen atom.

Among the compounds (17) and (18), a compound represented by the formula(17-ii):

wherein R¹ and R⁴ are as defined above, R^(4a-x) represents a halogenatom, R^(4c) represents the same meaning as that of R⁴, and n−2represents an integer of 0 to 2, can be produced, for example, accordingto the following Scheme (6).

In Scheme (6), R¹, R⁴, R^(4a-x), R^(4c) and n−2 are as defined above.

The compound (8) can be produced, for example, according to the processshown in the following Scheme (7).

In Scheme (7), J is as defined above, R¹⁷ represents a methyl group oran ethyl group, LDA represents lithium diisopropylamide, n-BuLirepresents normal butyl lithium, and t-BuLi represents tertiary butyllithium.

Among the compound (8), a compound represented by the formula (8-i)

wherein R^(13a), R^(14a), X^(a), Y^(a), Z^(a) and p are as definedabove, can be produced, for example, according to the process shown inthe following Scheme (8).

In Scheme (8), R^(13a), R^(14a), X^(a), Y^(a), Z^(a), p, LDA and n-BuLiare as defined above, and L⁵ represents a leaving group (e.g. a halogenatom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, amethylsulfonyl group etc.).

Among the compound (8), a compound represented by the formula (8-ii):

wherein R^(14a) and p are as defined above, R^(18a), R^(18b), R^(18c)and R^(18d), each, independently, represent a hydrogen atom, a halogenatom, a cyano group, a nitro group, a C1-C6 alkyl group optionallysubstituted with at least one halogen atom, a C1-C6 alkoxy groupoptionally substituted with at least one halogen atom, a C1-C6 alkylthiogroup optionally substituted with at least one halogen atom, a C1-C6alkylsulfinyl group optionally substituted with at least one halogenatom, or a C1-C6 alkylsulfonyl group optionally substituted with atleast one halogen atom, can be produced, for example, according to theprocess shown in the following Scheme (9).

In Scheme (9), R^(14a), R^(18a), R^(18b), R^(18c), R^(18d), LDA and pare as defined above, and L⁶ represents a leaving group (e.g. a halogenatom, a methylsulfonyl group etc.).

Among the compound (8), a compound represented by the formula (8-iii):

wherein R^(18a), R^(18b), R^(18c), R^(18d) and R^(18e) independentlyrepresent a hydrogen atom, a halogen atom, a cyano group, a nitro group,a C1-C6 alkyl group optionally substituted with at least one halogenatom, a C1-C6 alkoxy group optionally substituted with at least onehalogen atom, a C1-C6 alkylthio group optionally substituted with atleast one halogen atom, a C1-C6 alkylsulfinyl group optionallysubstituted with at least one halogen atom, or a C1-C6 alkylsulfonylgroup optionally substituted with at least one halogen atom, can beproduced, for example, according to the process shown in the followingScheme (10).

In Scheme (10), R^(18a), R^(18b), R^(18c), R^(18d) and R^(18e) are asdefined above.

Among the compound (8), a compound represented by the formula (8-iv):

wherein X¹⁸ represents —N═, or —CR^(18e)═; R^(18a), R^(18b), R^(18c),R^(18d) and R^(18e) are as defined above, and R^(14a-1) represents aC1-C6 alkyl group optionally substituted with at least one halogen atom,can be produced, for example, according to the process shown in thefollowing Scheme (11).

In Scheme (11), R^(14a-1), R¹⁷, R^(18a), R^(18b), R^(18c), R^(18d) andX¹⁸ are as defined above, and R²⁰ represents a methyl group or an ethylgroup.

Among the compound (8), a compound represented by the formula (8-vii):

wherein R^(13b), R^(14b), X^(b), Y^(b), Z^(b) and q are as definedabove, can be produced, for example, according to the process shown inthe following Scheme (14).

In Scheme (14), R^(13b), R^(14b), R¹⁷, X^(b), Y^(b), Z^(b), L⁵ and q areas defined above.

Among the compound (8), a compound represented by the formula (8-viii)and the formula (8-ix):

[wherein R^(13b) is as defined above,

X¹⁹ represents —N═, or —CR^(19e)═,

R^(19a), R^(19b), R^(19c), R^(19d) and R^(19e), each, independently,represent a hydrogen atom, a halogen atom, a cyano group, a nitro group,a C1-C6 alkyl group optionally substituted with at least one halogenatom, a C1-C6 alkoxy group optionally substituted with at least onehalogen atom, a C1-C6 alkylthio group optionally substituted with atleast one halogen atom, a C1-C6 alkylsulfinyl group optionallysubstituted with at least one halogen atom, or a C1-C6 alkylsulfonylgroup optionally substituted with at least one halogen atom]

can be produced, for example, according to the process shown in thefollowing Scheme (15).

In Scheme (15), R^(13b), R¹⁷, R^(19a), R^(19b), R^(19c), R^(19d), L⁵ andX¹⁹ are as defined above.

Among the compound (7), a compound represented by the formula (7-i):

wherein L² and J are as defined above, can be produced, for example,according to the process shown in the following Scheme (16).

In Scheme (16), L² and J are as defined above.

Among the compound (7), a compound represented by the formula (7-ii):

wherein L² and J are as defined above, can be produced, for example,according to the process shown in the following scheme (17).

In Scheme (17), L² and J are as defined above, LDA represents lithiumdiisopropylamide, n-BuLi represents normal butyl lithium, and t-BuLirepresents tertiary butyl lithium.

Among the compound (8), a compound represented by the formula (8-v):

wherein R^(18a), R^(18b), R^(18c), R^(18d) and X¹⁸ are as defined above,and R^(14ax), R^(14ay) and X^(14az) independently represent a hydrogenatom, a halogen atom, a cyano group, a C1-C6 alkyl group optionallysubstituted with at least one halogen atom, a C1-C6 alkoxy groupoptionally substituted with at least one halogen atom, a C1-C6 alkylthiogroup optionally substituted with at least one halogen atom, a C1-C6alkylsulfinyl group optionally substituted with at least one halogenatom, or a C1-C6 alkylsulfonyl group optionally substituted with atleast one halogen atom, can be produced, for example, according to theprocess shown in the following Scheme (18).

In Scheme (18), R^(18a), R^(18b), R^(18c), R^(18d), X¹⁸, R^(14ax),R^(14ay) and X^(14az) are as defined above.

The compounds (21) in scheme (18) can be produced, for example,according to the process shown in the following Scheme (19).

In Scheme (19), R^(18a), R^(18b), R^(18c), R^(18d), R^(18e), X¹⁸,R^(14ax), R^(14ay), X^(14az) and L⁶ are as defined above.

Among the compounds (21) in scheme (18), a compound represented by theformula (21-i), the formula (21-ii), and the formula (21-iii):

wherein R^(18a), R^(18b), R^(18c), R^(18d) and X¹⁸ are as defined above,and halo (x) and halo (y) independently represent a halogen atom, can beproduced, for example, according to the process shown in the followingScheme (20).

In Scheme (20), R^(18a), R^(18b), R^(18c), R^(18d), X¹⁸, halo (x) andhalo (y) are as defined above.

Among the compound (8), a compound represented by the formula (8-vi):

wherein R^(18a), R^(18b), R^(18c), R^(18d) and X¹⁸ are as defined above,R^(14ay-1) represents a hydrogen atom or a halogen atom, R³⁰ representsa C1-C6 alkyl group optionally substituted with at least one halogenatom, and r represents an integer of 0 to 2, can be produced, forexample, according to the process shown in the following Scheme (21).

In Scheme (21), R^(18a), R^(18b), R^(18c), R^(18d), X¹⁸, R^(14ay-1),R³⁰, r and L⁴ are as defined above.

The specific examples of the present compound are summarized in thefollowing tables.

A compound represented by the formula (1-A):

wherein R⁵, A³¹, (R⁴)_(n), R^(13a-1) and R^(14a-1) are combinationsshown in Table 1 to Table 7.

TABLE 1 R⁵ A³¹ (R⁴)_(n) R^(13a-1) R^(14a-1) H O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H H O 3-Br, 5-Cl 3-chloro-2-pyridinyl H H O 3-Br,5-Br 3-chloro-2-pyridinyl H H O 3-CH₃, 5-CN 3-chloro-2-pyridinyl H H O3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl H O 3-Br, 5-Cl 3-chloro-2-pyridinylCl H O 3-Br, 5-Br 3-chloro-2-pyridinyl Cl H O 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl H O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br H O3-Br, 5-Cl 3-chloro-2-pyridinyl Br H O 3-Br, 5-Br 3-chloro-2-pyridinylBr H O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br H O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ H O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ H O3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ H O 3-CH₃, 5-CN 3-chloro-2-pyridinylCF₃ CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl H CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl H CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl H CH₃ O3-CH₃, 5-CN 3-chloro-2-pyridinyl H CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl CH₃ O3-Br, 5-Br 3-chloro-2-pyridinyl Cl CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br CH₃ O3-Br, 5-Cl 3-chloro-2-pyridinyl Br CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinylBr CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₃ O3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃

TABLE 2 R⁵ A³¹ (R⁴)_(n) R^(13a-1) R^(14a-1) CH₂CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H CH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl H CH₂CH₃O 3-Br, 5-Br 3-chloro-2-pyridinyl H CH₂CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl H CH₂CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl ClCH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl CH₂CH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl Cl CH₂CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl ClCH₂CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br CH₂CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl Br CH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl BrCH₂CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br CH₂CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ CH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃CH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ CH₂CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃ CH(CH₃)₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl HCH(CH₃)₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl H CH(CH₃)₂ O 3-Br, 5-Br3-chloro-2-pyridinyl H CH(CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl HCH(CH₃)₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl CH(CH₃)₂ O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl CH(CH₃)₂ O 3-Br, 5-Br 3-chloro-2-pyridinyl ClCH(CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl CH(CH₃)₂ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br CH(CH₃)₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl BrCH(CH₃)₂ O 3-Br, 5-Br 3-chloro-2-pyridinyl Br CH(CH₃)₂ O 3-CH₃, 5-CN3-chloro-2-pyridinyl Br CH(CH₃)₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃CH(CH₃)₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ CH(CH₃)₂ O 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ CH(CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

TABLE 3 R⁵ A³¹ (R⁴)_(n) R^(13a-1) R^(14a-1) C(CH₃)₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H C(CH₃)₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl HC(CH₃)₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl H C(CH₃)₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl H C(CH₃)₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl ClC(CH₃)₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl C(CH₃)₃ O 3-Br, 5-Br3-chloro-2-pyridinyl Cl C(CH₃)₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl ClC(CH₃)₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br C(CH₃)₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl Br C(CH₃)₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl BrC(CH₃)₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br C(CH₃)₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ C(CH₃)₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃C(CH₃)₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ C(CH₃)₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃ CF₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl H CF₃ O3-Br, 5-Cl 3-chloro-2-pyridinyl H CF₃ O 3-Br, 5-Br 3-chloro-2-pyridinylH CF₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl H CF₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl CF₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl CF₃ O3-Br, 5-Br 3-chloro-2-pyridinyl Cl CF₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl CF₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br CF₃ O3-Br, 5-Cl 3-chloro-2-pyridinyl Br CF₃ O 3-Br, 5-Br 3-chloro-2-pyridinylBr CF₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br CF₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ CF₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ CF₃ O3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ CF₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃

TABLE 4 R⁵ A³¹ (R⁴)_(n) R^(13a-1) R^(14a-1) CH₂OCH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H CH₂OCH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl HCH₂OCH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl H CH₂OCH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl H CH₂OCH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl ClCH₂OCH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl CH₂OCH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl Cl CH₂OCH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl ClCH₂OCH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br CH₂OCH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl Br CH₂OCH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl BrCH₂OCH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br CH₂OCH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ CH₂OCH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃CH₂OCH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ CH₂OCH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃ CH₂SCH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl HCH₂SCH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl H CH₂SCH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl H CH₂SCH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl HCH₂SCH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl CH₂SCH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl CH₂SCH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl ClCH₂SCH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl CH₂SCH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br CH₂SCH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl BrCH₂SCH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl Br CH₂SCH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl Br CH₂SCH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃CH₂SCH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₂SCH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ CH₂SCH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

TABLE 5 R⁵ A³¹ (R⁴)_(n) R^(13a-1) R^(14a-1) CH₂N(CH₃)₂ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H CH₂N(CH₃)₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl HCH₂N(CH₃)₂ O 3-Br, 5-Br 3-chloro-2-pyridinyl H CH₂N(CH₃)₂ O 3-CH₃, 5-CN3-chloro-2-pyridinyl H CH₂N(CH₃)₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl ClCH₂N(CH₃)₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl CH₂N(CH₃)₂ O 3-Br, 5-Br3-chloro-2-pyridinyl Cl CH₂N(CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl ClCH₂N(CH₃)₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br CH₂N(CH₃)₂ O 3-Br, 5-Cl3-chloro-2-pyridinyl Br CH₂N(CH₃)₂ O 3-Br, 5-Br 3-chloro-2-pyridinyl BrCH₂N(CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br CH₂N(CH₃)₂ O 3-CH₃,5-Cl 3-chloro-2-pyridinyl CF₃ CH₂N(CH₃)₂ O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ CH₂N(CH₃)₂ O 3-Br, 5-Br 3-chloro-2-pyridinylCF₃ CH₂N(CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃ cyclopropyl O3-CH₃, 5-Cl 3-chloro-2-pyridinyl H cyclopropyl O 3-Br, 5-Cl3-chloro-2-pyridinyl H cyclopropyl O 3-Br, 5-Br 3-chloro-2-pyridinyl Hcyclopropyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl H cyclopropyl O 3-CH₃,5-Cl 3-chloro-2-pyridinyl Cl cyclopropyl O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl cyclopropyl O 3-Br, 5-Br 3-chloro-2-pyridinyl Clcyclopropyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl cyclopropyl O 3-CH₃,5-Cl 3-chloro-2-pyridinyl Br cyclopropyl O 3-Br, 5-Cl3-chloro-2-pyridinyl Br cyclopropyl O 3-Br, 5-Br 3-chloro-2-pyridinyl Brcyclopropyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br cyclopropyl O 3-CH₃,5-Cl 3-chloro-2-pyridinyl CF₃ cyclopropyl O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ cyclopropyl O 3-Br, 5-Br 3-chloro-2-pyridinylCF₃ cyclopropyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

TABLE 6 R⁵ A³¹ (R⁴)_(n) R^(13a-1) R^(14a-1) cyclobutyl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H cyclobutyl O 3-Br, 5-Cl 3-chloro-2-pyridinyl Hcyclobutyl O 3-Br, 5-Br 3-chloro-2-pyridinyl H cyclobutyl O 3-CH₃, 5-CN3-chloro-2-pyridinyl H cyclobutyl O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Clcyclobutyl O 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl cyclobutyl O 3-Br, 5-Br3-chloro-2-pyridinyl Cl cyclobutyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Clcyclobutyl O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br cyclobutyl O 3-Br, 5-Cl3-chloro-2-pyridinyl Br cyclobutyl O 3-Br, 5-Br 3-chloro-2-pyridinyl Brcyclobutyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br cyclobutyl O 3-CH₃,5-Cl 3-chloro-2-pyridinyl CF₃ cyclobutyl O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ cyclobutyl O 3-Br, 5-Br 3-chloro-2-pyridinylCF₃ cyclobutyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃ cyclopentyl O3-CH₃, 5-Cl 3-chloro-2-pyridinyl H cyclopentyl O 3-Br, 5-Cl3-chloro-2-pyridinyl H cyclopentyl O 3-Br, 5-Br 3-chloro-2-pyridinyl Hcyclopentyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl H cyclopentyl O 3-CH₃,5-Cl 3-chloro-2-pyridinyl Cl cyclopentyl O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl cyclopentyl O 3-Br, 5-Br 3-chloro-2-pyridinyl Clcyclopentyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl cyclopentyl O 3-CH₃,5-Cl 3-chloro-2-pyridinyl Br cyclopentyl O 3-Br, 5-Cl3-chloro-2-pyridinyl Br cyclopentyl O 3-Br, 5-Br 3-chloro-2-pyridinyl Brcyclopentyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br cyclopentyl O 3-CH₃,5-Cl 3-chloro-2-pyridinyl CF₃ cyclopentyl O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ cyclopentyl O 3-Br, 5-Br 3-chloro-2-pyridinylCF₃ cyclopentyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

TABLE 7 R⁵ A³¹ (R⁴)_(n) R^(13a-1) R^(14a-1) cyclohexyl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H cyclohexyl O 3-Br, 5-Cl 3-chloro-2-pyridinyl Hcyclohexyl O 3-Br, 5-Br 3-chloro-2-pyridinyl H cyclohexyl O 3-CH₃, 5-CN3-chloro-2-pyridinyl H cyclohexyl O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Clcyclohexyl O 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl cyclohexyl O 3-Br, 5-Br3-chloro-2-pyridinyl Cl cyclohexyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Clcyclohexyl O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br cyclohexyl O 3-Br, 5-Cl3-chloro-2-pyridinyl Br cyclohexyl O 3-Br, 5-Br 3-chloro-2-pyridinyl Brcyclohexyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br cyclohexyl O 3-CH₃,5-Cl 3-chloro-2-pyridinyl CF₃ cyclohexyl O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ cyclohexyl O 3-Br, 5-Br 3-chloro-2-pyridinylCF₃ cyclohexyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃ phenyl O 3-CH₃,5-Cl 3-chloro-2-pyridinyl H phenyl O 3-Br, 5-Cl 3-chloro-2-pyridinyl Hphenyl O 3-Br, 5-Br 3-chloro-2-pyridinyl H phenyl O 3-CH₃, 5-CN3-chloro-2-pyridinyl H phenyl O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Clphenyl O 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl phenyl O 3-Br, 5-Br3-chloro-2-pyridinyl Cl phenyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Clphenyl O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br phenyl O 3-Br, 5-Cl3-chloro-2-pyridinyl Br phenyl O 3-Br, 5-Br 3-chloro-2-pyridinyl Brphenyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br phenyl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ phenyl O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃phenyl O 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ phenyl O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃

A compound represented by the formula (1-B):

wherein R⁶, A³², (R⁴)_(n), R^(13a-1) and R^(14a-1) representcombinations shown in Table 8 to Table 31.

TABLE 8 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ O 3-CH₃3-chloro-2-pyridinyl H CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl H CH₃ O3-CH₃, 5-Br 3-chloro-2-pyridinyl H CH₃ O 3-CH₃, 5-I 3-chloro-2-pyridinylH CH₃ O 3-CH₃, 5-CH₃ 3-chloro-2-pyridinyl H CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl H CH₃ O 3-Cl 3-chloro-2-pyridinyl H CH₃ O 3-Cl,5-Cl 3-chloro-2-pyridinyl H CH₃ O 3-Cl, 5-Br 3-chloro-2-pyridinyl H CH₃O 3-Cl, 5-I 3-chloro-2-pyridinyl H CH₃ O 3-Cl, 5-CH₃3-chloro-2-pyridinyl H CH₃ O 3-Cl, 5-CN 3-chloro-2-pyridinyl H CH₃ O3-Br 3-chloro-2-pyridinyl H CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl H CH₃O 3-Br, 5-Br 3-chloro-2-pyridinyl H CH₃ O 3-Br, 5-I 3-chloro-2-pyridinylH CH₃ O 3-Br, 5-CH₃ 3-chloro-2-pyridinyl H CH₃ O 3-Br, 5-CN3-chloro-2-pyridinyl H CH₃ O 3-I 3-chloro-2-pyridinyl H CH₃ O 3-I, 5-Cl3-chloro-2-pyridinyl H CH₃ O 3-I, 5-Br 3-chloro-2-pyridinyl H CH₃ O 3-I,5-I 3-chloro-2-pyridinyl H CH₃ O 3-I, 5-CH₃ 3-chloro-2-pyridinyl H CH₃ O3-I, 5-CN 3-chloro-2-pyridinyl H

TABLE 9 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ O 3-CH₃3-chloro-2-pyridinyl F CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl F CH₃ O3-CH₃, 5-Br 3-chloro-2-pyridinyl F CH₃ O 3-CH₃, 5-I 3-chloro-2-pyridinylF CH₃ O 3-CH₃, 5-CH₃ 3-chloro-2-pyridinyl F CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl F CH₃ O 3-Cl 3-chloro-2-pyridinyl F CH₃ O 3-Cl,5-Cl 3-chloro-2-pyridinyl F CH₃ O 3-Cl, 5-Br 3-chloro-2-pyridinyl F CH₃O 3-Cl, 5-I 3-chloro-2-pyridinyl F CH₃ O 3-Cl, 5-CH₃3-chloro-2-pyridinyl F CH₃ O 3-Cl, 5-CN 3-chloro-2-pyridinyl F CH₃ O3-Br 3-chloro-2-pyridinyl F CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl F CH₃O 3-Br, 5-Br 3-chloro-2-pyridinyl F CH₃ O 3-Br, 5-I 3-chloro-2-pyridinylF CH₃ O 3-Br, 5-CH₃ 3-chloro-2-pyridinyl F CH₃ O 3-Br, 5-CN3-chloro-2-pyridinyl F CH₃ O 3-I 3-chloro-2-pyridinyl F CH₃ O 3-I, 5-Cl3-chloro-2-pyridinyl F CH₃ O 3-I, 5-Br 3-chloro-2-pyridinyl F CH₃ O 3-I,5-I 3-chloro-2-pyridinyl F CH₃ O 3-I, 5-CH₃ 3-chloro-2-pyridinyl F CH₃ O3-I, 5-CN 3-chloro-2-pyridinyl F

TABLE 10 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ O 3-CH₃3-chloro-2-pyridinyl Cl CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl CH₃ O3-CH₃, 5-Br 3-chloro-2-pyridinyl Cl CH₃ O 3-CH₃, 5-I3-chloro-2-pyridinyl Cl CH₃ O 3-CH₃, 5-CH₃ 3-chloro-2-pyridinyl Cl CH₃ O3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl CH₃ O 3-Cl 3-chloro-2-pyridinyl ClCH₃ O 3-Cl, 5-Cl 3-chloro-2-pyridinyl Cl CH₃ O 3-Cl, 5-Br3-chloro-2-pyridinyl Cl CH₃ O 3-Cl, 5-I 3-chloro-2-pyridinyl Cl CH₃ O3-Cl, 5-CH₃ 3-chloro-2-pyridinyl Cl CH₃ O 3-Cl, 5-CN3-chloro-2-pyridinyl Cl CH₃ O 3-Br 3-chloro-2-pyridinyl Cl CH₃ O 3-Br,5-Cl 3-chloro-2-pyridinyl Cl CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl ClCH₃ O 3-Br, 5-I 3-chloro-2-pyridinyl Cl CH₃ O 3-Br, 5-CH₃3-chloro-2-pyridinyl Cl CH₃ O 3-Br, 5-CN 3-chloro-2-pyridinyl Cl CH₃ O3-I 3-chloro-2-pyridinyl Cl CH₃ O 3-I, 5-Cl 3-chloro-2-pyridinyl Cl CH₃O 3-I, 5-Br 3-chloro-2-pyridinyl Cl CH₃ O 3-I, 5-I 3-chloro-2-pyridinylCl CH₃ O 3-I, 5-CH₃ 3-chloro-2-pyridinyl Cl CH₃ O 3-I, 5-CN3-chloro-2-pyridinyl Cl

TABLE 11 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ O 3-CH₂CH₃3-chloro-2-pyridinyl Cl CH₃ O 3-CH(CH₃)₂ 3-chloro-2-pyridinyl Cl CH₃ O3-C(CH₃)₃ 3-chloro-2-pyridinyl Cl CH₃ O 3-CF₃ 3-chloro-2-pyridinyl ClCH₃ O 3-OCH₃ 3-chloro-2-pyridinyl Cl CH₃ O 3-phenyl 3-chloro-2-pyridinylCl CH₃ O 3-CH₂CH₃, 5-Cl 3-chloro-2-pyridinyl Cl CH₃ O 3-CH(CH₃)₂, 5-Cl3-chloro-2-pyridinyl Cl CH₃ O 3-C(CH₃)₃, 5-Cl 3-chloro-2-pyridinyl ClCH₃ O 3-CF₃, 5-Cl 3-chloro-2-pyridinyl Cl CH₃ O 3-OCH₃, 5-Cl3-chloro-2-pyridinyl Cl CH₃ O 3-phenyl, 5-Cl 3-chloro-2-pyridinyl Cl CH₃O 3-CH₃, 4-Cl 3-chloro-2-pyridinyl Cl CH₃ O 3-Cl, 4-Cl3-chloro-2-pyridinyl Cl CH₃ O 3-CH₃, 6-Cl 3-chloro-2-pyridinyl Cl CH₃ O3-Cl, 6-Cl 3-chloro-2-pyridinyl Cl CH₃ O 3-CH₃, 4-Cl, 5-Cl3-chloro-2-pyridinyl Cl CH₃ O 3-Cl, 4-Cl, 5-Cl 3-chloro-2-pyridinyl ClCH₃ O 3-CH₃, 5-Cl, 6-Cl 3-chloro-2-pyridinyl Cl CH₃ O 3-Cl, 5-Cl, 6-Cl3-chloro-2-pyridinyl Cl CH₃ O 3-CH₃, 5-F 3-chloro-2-pyridinyl Cl CH₃ O3-Cl, 5-F 3-chloro-2-pyridinyl Cl CH₃ O 3-Br, 5-F 3-chloro-2-pyridinylCl CH₃ O 3-I, 5-F 3-chloro-2-pyridinyl Cl CH₃ O 3-Me,4,5-CH═CH—CH═CH—3-chloro-2-pyridinyl Cl CH₃ O 3-Cl,4,5-CH═CH—CH═CH— 3-chloro-2-pyridinylCl CH₃ O 3-Br,4,5-CH═CH—CH═CH— 3-chloro-2-pyridinyl Cl CH₃ O3-I,4,5-CH═CH—CH═CH— 3-chloro-2-pyridinyl Cl

TABLE 12 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ O 3-CH₃3-chloro-2-pyridinyl Br CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br CH₃ O3-CH₃, 5-Br 3-chloro-2-pyridinyl Br CH₃ O 3-CH₃, 5-I3-chloro-2-pyridinyl Br CH₃ O 3-CH₃, 5-CH₃ 3-chloro-2-pyridinyl Br CH₃ O3-CH₃, 5-CN 3-chloro-2-pyridinyl Br CH₃ O 3-Cl 3-chloro-2-pyridinyl BrCH₃ O 3-Cl, 5-Cl 3-chloro-2-pyridinyl Br CH₃ O 3-Cl, 5-Br3-chloro-2-pyridinyl Br CH₃ O 3-Cl, 5-I 3-chloro-2-pyridinyl Br CH₃ O3-Cl, 5-CH₃ 3-chloro-2-pyridinyl Br CH₃ O 3-Cl, 5-CN3-chloro-2-pyridinyl Br CH₃ O 3-Br 3-chloro-2-pyridinyl Br CH₃ O 3-Br,5-Cl 3-chloro-2-pyridinyl Br CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl BrCH₃ O 3-Br, 5-I 3-chloro-2-pyridinyl Br CH₃ O 3-Br, 5-CH₃3-chloro-2-pyridinyl Br CH₃ O 3-Br, 5-CN 3-chloro-2-pyridinyl Br CH₃ O3-I 3-chloro-2-pyridinyl Br CH₃ O 3-I, 5-Cl 3-chloro-2-pyridinyl Br CH₃O 3-I, 5-Br 3-chloro-2-pyridinyl Br CH₃ O 3-I, 5-I 3-chloro-2-pyridinylBr CH₃ O 3-I, 5-CH₃ 3-chloro-2-pyridinyl Br CH₃ O 3-I, 5-CN3-chloro-2-pyridinyl Br

TABLE 13 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ O 3-CH₂CH₃3-chloro-2-pyridinyl Br CH₃ O 3-CH(CH₃)₂ 3-chloro-2-pyridinyl Br CH₃ O3-C(CH₃)₃ 3-chloro-2-pyridinyl Br CH₃ O 3-CF₃ 3-chloro-2-pyridinyl BrCH₃ O 3-OCH₃ 3-chloro-2-pyridinyl Br CH₃ O 3-phenyl 3-chloro-2-pyridinylBr CH₃ O 3-CH₂CH₃, 5-Cl 3-chloro-2-pyridinyl Br CH₃ O 3-CH(CH₃)₂, 5-Cl3-chloro-2-pyridinyl Br CH₃ O 3-C(CH₃)₃, 5-Cl 3-chloro-2-pyridinyl BrCH₃ O 3-CF₃, 5-Cl 3-chloro-2-pyridinyl Br CH₃ O 3-OCH₃, 5-Cl3-chloro-2-pyridinyl Br CH₃ O 3-phenyl, 5-Cl 3-chloro-2-pyridinyl Br CH₃O 3-CH₃, 4-Cl 3-chloro-2-pyridinyl Br CH₃ O 3-Cl, 4-Cl3-chloro-2-pyridinyl Br CH₃ O 3-CH₃, 6-Cl 3-chloro-2-pyridinyl Br CH₃ O3-Cl, 6-Cl 3-chloro-2-pyridinyl Br CH₃ O 3-CH₃, 4-Cl, 5-Cl3-chloro-2-pyridinyl Br CH₃ O 3-Cl, 4-Cl, 5-Cl 3-chloro-2-pyridinyl BrCH₃ O 3-CH₃, 5-Cl, 6-Cl 3-chloro-2-pyridinyl Br CH₃ O 3-Cl, 5-Cl, 6-Cl3-chloro-2-pyridinyl Br CH₃ O 3-CH₃, 5-F 3-chloro-2-pyridinyl Br CH₃ O3-Cl, 5-F 3-chloro-2-pyridinyl Br CH₃ O 3-Br, 5-F 3-chloro-2-pyridinylBr CH₃ O 3-I, 5-F 3-chloro-2-pyridinyl Br CH₃ O 3-Me,4,5-CH═CH—CH═CH—3-chloro-2-pyridinyl Br CH₃ O 3-Cl,4,5-CH═CH—CH═CH— 3-chloro-2-pyridinylBr CH₃ O 3-Br,4,5-CH═CH—CH═CH— 3-chloro-2-pyridinyl Br CH₃ O3-I,4,5-CH═CH—CH═CH— 3-chloro-2-pyridinyl Br

TABLE 14 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ O 3-CH₃3-chloro-2-pyridinyl I CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl I CH₃ O3-CH₃, 5-Br 3-chloro-2-pyridinyl I CH₃ O 3-CH₃, 5-I 3-chloro-2-pyridinylI CH₃ O 3-CH₃, 5-CH₃ 3-chloro-2-pyridinyl I CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl I CH₃ O 3-Cl 3-chloro-2-pyridinyl I CH₃ O 3-Cl,5-Cl 3-chloro-2-pyridinyl I CH₃ O 3-Cl, 5-Br 3-chloro-2-pyridinyl I CH₃O 3-Cl, 5-I 3-chloro-2-pyridinyl I CH₃ O 3-Cl, 5-CH₃3-chloro-2-pyridinyl I CH₃ O 3-Cl, 5-CN 3-chloro-2-pyridinyl I CH₃ O3-Br 3-chloro-2-pyridinyl I CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl I CH₃O 3-Br, 5-Br 3-chloro-2-pyridinyl I CH₃ O 3-Br, 5-I 3-chloro-2-pyridinylI CH₃ O 3-Br, 5-CH₃ 3-chloro-2-pyridinyl I CH₃ O 3-Br, 5-CN3-chloro-2-pyridinyl I CH₃ O 3-I 3-chloro-2-pyridinyl I CH₃ O 3-I, 5-Cl3-chloro-2-pyridinyl I CH₃ O 3-I, 5-Br 3-chloro-2-pyridinyl I CH₃ O 3-I,5-I 3-chloro-2-pyridinyl I CH₃ O 3-I, 5-CH₃ 3-chloro-2-pyridinyl I CH₃ O3-I, 5-CN 3-chloro-2-pyridinyl I

TABLE 15 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ O 3-CH₃3-chloro-2-pyridinyl CH₃ CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CH₃ CH₃O 3-CH₃, 5-Br 3-chloro-2-pyridinyl CH₃ CH₃ O 3-CH₃, 5-I3-chloro-2-pyridinyl CH₃ CH₃ O 3-CH₃, 5-CH₃ 3-chloro-2-pyridinyl CH₃ CH₃O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CH₃ CH₃ O 3-Cl 3-chloro-2-pyridinylCH₃ CH₃ O 3-Cl, 5-Cl 3-chloro-2-pyridinyl CH₃ CH₃ O 3-Cl, 5-Br3-chloro-2-pyridinyl CH₃ CH₃ O 3-Cl, 5-I 3-chloro-2-pyridinyl CH₃ CH₃ O3-Cl, 5-CH₃ 3-chloro-2-pyridinyl CH₃ CH₃ O 3-Cl, 5-CN3-chloro-2-pyridinyl CH₃ CH₃ O 3-Br 3-chloro-2-pyridinyl CH₃ CH₃ O 3-Br,5-Cl 3-chloro-2-pyridinyl CH₃ CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl CH₃CH₃ O 3-Br, 5-I 3-chloro-2-pyridinyl CH₃ CH₃ O 3-Br, 5-CH₃3-chloro-2-pyridinyl CH₃ CH₃ O 3-Br, 5-CN 3-chloro-2-pyridinyl CH₃ CH₃ O3-I 3-chloro-2-pyridinyl CH₃ CH₃ O 3-I, 5-Cl 3-chloro-2-pyridinyl CH₃CH₃ O 3-I, 5-Br 3-chloro-2-pyridinyl CH₃ CH₃ O 3-I, 5-I3-chloro-2-pyridinyl CH₃ CH₃ O 3-I, 5-CH₃ 3-chloro-2-pyridinyl CH₃ CH₃ O3-I, 5-CN 3-chloro-2-pyridinyl CH₃

TABLE 16 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ O 3-CH₃3-chloro-2-pyridinyl CF₃ CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₃O 3-CH₃, 5-Br 3-chloro-2-pyridinyl CF₃ CH₃ O 3-CH₃, 5-I3-chloro-2-pyridinyl CF₃ CH₃ O 3-CH₃, 5-CH₃ 3-chloro-2-pyridinyl CF₃ CH₃O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃ CH₃ O 3-Cl 3-chloro-2-pyridinylCF₃ CH₃ O 3-Cl, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₃ O 3-Cl, 5-Br3-chloro-2-pyridinyl CF₃ CH₃ O 3-Cl, 5-I 3-chloro-2-pyridinyl CF₃ CH₃ O3-Cl, 5-CH₃ 3-chloro-2-pyridinyl CF₃ CH₃ O 3-Cl, 5-CN3-chloro-2-pyridinyl CF₃ CH₃ O 3-Br 3-chloro-2-pyridinyl CF₃ CH₃ O 3-Br,5-Cl 3-chloro-2-pyridinyl CF₃ CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃CH₃ O 3-Br, 5-I 3-chloro-2-pyridinyl CF₃ CH₃ O 3-Br, 5-CH₃3-chloro-2-pyridinyl CF₃ CH₃ O 3-Br, 5-CN 3-chloro-2-pyridinyl CF₃ CH₃ O3-I 3-chloro-2-pyridinyl CF₃ CH₃ O 3-I, 5-Cl 3-chloro-2-pyridinyl CF₃CH₃ O 3-I, 5-Br 3-chloro-2-pyridinyl CF₃ CH₃ O 3-I, 5-I3-chloro-2-pyridinyl CF₃ CH₃ O 3-I, 5-CH₃ 3-chloro-2-pyridinyl CF₃ CH₃ O3-I, 5-CN 3-chloro-2-pyridinyl CF₃

TABLE 17 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ O 3-CH₂CH₃3-chloro-2-pyridinyl CF₃ CH₃ O 3-CH(CH₃)₂ 3-chloro-2-pyridinyl CF₃ CH₃ O3-C(CH₃)₃ 3-chloro-2-pyridinyl CF₃ CH₃ O 3-CF₃ 3-chloro-2-pyridinyl CF₃CH₃ O 3-OCH₃ 3-chloro-2-pyridinyl CF₃ CH₃ O 3-phenyl3-chloro-2-pyridinyl CF₃ CH₃ O 3-CH₂CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃CH₃ O 3-CH(CH₃)₂, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₃ O 3-C(CH₃)₃, 5-Cl3-chloro-2-pyridinyl CF₃ CH₃ O 3-CF₃, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₃O 3-OCH₃, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₃ O 3-phenyl, 5-Cl3-chloro-2-pyridinyl CF₃ CH₃ O 3-CH₃, 4-Cl 3-chloro-2-pyridinyl CF₃ CH₃O 3-Cl, 4-Cl 3-chloro-2-pyridinyl CF₃ CH₃ O 3-CH₃, 6-Cl3-chloro-2-pyridinyl CF₃ CH₃ O 3-Cl, 6-Cl 3-chloro-2-pyridinyl CF₃ CH₃ O3-CH₃, 4-Cl, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₃ O 3-Cl, 4-Cl, 5-Cl3-chloro-2-pyridinyl CF₃ CH₃ O 3-CH₃, 5-Cl, 6-Cl 3-chloro-2-pyridinylCF₃ CH₃ O 3-Cl, 5-Cl, 6-Cl 3-chloro-2-pyridinyl CF₃ CH₃ O 3-CH₃, 5-F3-chloro-2-pyridinyl CF₃ CH₃ O 3-Cl, 5-F 3-chloro-2-pyridinyl CF₃ CH₃ O3-Br, 5-F 3-chloro-2-pyridinyl CF₃ CH₃ O 3-I, 5-F 3-chloro-2-pyridinylCF₃ CH₃ O 3-Me,4,5-CH═CH—CH═CH— 3-chloro-2-pyridinyl CF₃ CH₃ O3-Cl,4,5-CH═CH—CH═CH— 3-chloro-2-pyridinyl CF₃ CH₃ O3-Br,4,5-CH═CH—CH═CH— 3-chloro-2-pyridinyl CF₃ CH₃ O3-I,4,5-CH═CH—CH═CH— 3-chloro-2-pyridinyl CF₃

TABLE 18 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ O 3-CH₃3-chloro-2-pyridinyl SCH₃ CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl SCH₃CH₃ O 3-CH₃, 5-Br 3-chloro-2-pyridinyl SCH₃ CH₃ O 3-CH₃, 5-I3-chloro-2-pyridinyl SCH₃ CH₃ O 3-CH₃, 5-CH₃ 3-chloro-2-pyridinyl SCH₃CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl SCH₃ CH₃ O 3-Cl3-chloro-2-pyridinyl SCH₃ CH₃ O 3-Cl, 5-Cl 3-chloro-2-pyridinyl SCH₃ CH₃O 3-Cl, 5-Br 3-chloro-2-pyridinyl SCH₃ CH₃ O 3-Cl, 5-I3-chloro-2-pyridinyl SCH₃ CH₃ O 3-Cl, 5-CH₃ 3-chloro-2-pyridinyl SCH₃CH₃ O 3-Cl, 5-CN 3-chloro-2-pyridinyl SCH₃ CH₃ O 3-Br3-chloro-2-pyridinyl SCH₃ CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl SCH₃ CH₃O 3-Br, 5-Br 3-chloro-2-pyridinyl SCH₃ CH₃ O 3-Br, 5-I3-chloro-2-pyridinyl SCH₃ CH₃ O 3-Br, 5-CH₃ 3-chloro-2-pyridinyl SCH₃CH₃ O 3-Br, 5-CN 3-chloro-2-pyridinyl SCH₃ CH₃ O 3-I3-chloro-2-pyridinyl SCH₃ CH₃ O 3-I, 5-Cl 3-chloro-2-pyridinyl SCH₃ CH₃O 3-I, 5-Br 3-chloro-2-pyridinyl SCH₃ CH₃ O 3-I, 5-I3-chloro-2-pyridinyl SCH₃ CH₃ O 3-I, 5-CH₃ 3-chloro-2-pyridinyl SCH₃ CH₃O 3-I, 5-CN 3-chloro-2-pyridinyl SCH₃

TABLE 19 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ O 3-CH₃3-chloro-2-pyridinyl S(═O)CH₃ CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinylS(═O)CH₃ CH₃ O 3-CH₃, 5-Br 3-chloro-2-pyridinyl S(═O)CH₃ CH₃ O 3-CH₃,5-I 3-chloro-2-pyridinyl S(═O)CH₃ CH₃ O 3-CH₃, 5-CH₃3-chloro-2-pyridinyl S(═O)CH₃ CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinylS(═O)CH₃ CH₃ O 3-Cl 3-chloro-2-pyridinyl S(═O)CH₃ CH₃ O 3-Cl, 5-Cl3-chloro-2-pyridinyl S(═O)CH₃ CH₃ O 3-Cl, 5-Br 3-chloro-2-pyridinylS(═O)CH₃ CH₃ O 3-Cl, 5-I 3-chloro-2-pyridinyl S(═O)CH₃ CH₃ O 3-Cl, 5-CH₃3-chloro-2-pyridinyl S(═O)CH₃ CH₃ O 3-Cl, 5-CN 3-chloro-2-pyridinylS(═O)CH₃ CH₃ O 3-Br 3-chloro-2-pyridinyl S(═O)CH₃ CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl S(═O)CH₃ CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinylS(═O)CH₃ CH₃ O 3-Br, 5-I 3-chloro-2-pyridinyl S(═O)CH₃ CH₃ O 3-Br, 5-CH₃3-chloro-2-pyridinyl S(═O)CH₃ CH₃ O 3-Br, 5-CN 3-chloro-2-pyridinylS(═O)CH₃ CH₃ O 3-I 3-chloro-2-pyridinyl S(═O)CH₃ CH₃ O 3-I, 5-Cl3-chloro-2-pyridinyl S(═O)CH₃ CH₃ O 3-I, 5-Br 3-chloro-2-pyridinylS(═O)CH₃ CH₃ O 3-I, 5-I 3-chloro-2-pyridinyl S(═O)CH₃ CH₃ O 3-I, 5-CH₃3-chloro-2-pyridinyl S(═O)CH₃ CH₃ O 3-I, 5-CN 3-chloro-2-pyridinylS(═O)CH₃

TABLE 20 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ O 3-CH₃3-chloro-2-pyridinyl S(═O)₂CH₃ CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinylS(═O)₂CH₃ CH₃ O 3-CH₃, 5-Br 3-chloro-2-pyridinyl S(═O)₂CH₃ CH₃ O 3-CH₃,5-I 3-chloro-2-pyridinyl S(═O)₂CH₃ CH₃ O 3-CH₃, 5-CH₃3-chloro-2-pyridinyl S(═O)₂CH₃ CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinylS(═O)₂CH₃ CH₃ O 3-Cl 3-chloro-2-pyridinyl S(═O)₂CH₃ CH₃ O 3-Cl, 5-Cl3-chloro-2-pyridinyl S(═O)₂CH₃ CH₃ O 3-Cl, 5-Br 3-chloro-2-pyridinylS(═O)₂CH₃ CH₃ O 3-Cl, 5-I 3-chloro-2-pyridinyl S(═O)₂CH₃ CH₃ O 3-Cl,5-CH₃ 3-chloro-2-pyridinyl S(═O)₂CH₃ CH₃ O 3-Cl, 5-CN3-chloro-2-pyridinyl S(═O)₂CH₃ CH₃ O 3-Br 3-chloro-2-pyridinyl S(═O)₂CH₃CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl S(═O)₂CH₃ CH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl S(═O)₂CH₃ CH₃ O 3-Br, 5-I 3-chloro-2-pyridinylS(═O)₂CH₃ CH₃ O 3-Br, 5-CH₃ 3-chloro-2-pyridinyl S(═O)₂CH₃ CH₃ O 3-Br,5-CN 3-chloro-2-pyridinyl S(═O)₂CH₃ CH₃ O 3-I 3-chloro-2-pyridinylS(═O)₂CH₃ CH₃ O 3-I, 5-Cl 3-chloro-2-pyridinyl S(═O)₂CH₃ CH₃ O 3-I, 5-Br3-chloro-2-pyridinyl S(═O)₂CH₃ CH₃ O 3-I, 5-I 3-chloro-2-pyridinylS(═O)₂CH₃ CH₃ O 3-I, 5-CH₃ 3-chloro-2-pyridinyl S(═O)₂CH₃ CH₃ O 3-I,5-CN 3-chloro-2-pyridinyl S(═O)₂CH₃

TABLE 21 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl SCH₂CH₃ CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinylSCH₂CH₃ CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl SCH₂CH₃ CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl SCH₂CH₃ CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinylSCH(CH₃)₂ CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl SCH(CH₃)₂ CH₃ O 3-Br,5-Br 3-chloro-2-pyridinyl SCH(CH₃)₂ CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl SCH(CH₃)₂ CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinylOCH₃ CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl OCH₃ CH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl OCH₃ CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl OCH₃CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl OCH₂CF₃ CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl OCH₂CF₃ CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinylOCH₂CF₃ CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl OCH₂CF₃ CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CH₂CH₃ CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl CH₂CH₃CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl CH₂CH₃ CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl CH₂CH₃ CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinylCH(CH₃)₂ CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl CH(CH₃)₂ CH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl CH(CH₃)₂ CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinylCH(CH₃)₂ CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl C(CH₃)₃ CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl C(CH₃)₃ CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinylC(CH₃)₃ CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl C(CH₃)₃ CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CN CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl CN CH₃ O3-Br, 5-Br 3-chloro-2-pyridinyl CN CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl CN

TABLE 22 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ O 3-CH₃, 5-Cl3-fluoro-2-pyridinyl H CH₃ O 3-Br, 5-Cl 3-fluoro-2-pyridinyl H CH₃ O3-Br, 5-Br 3-fluoro-2-pyridinyl H CH₃ O 3-CH₃, 5-CN 3-fluoro-2-pyridinylH CH₃ O 3-CH₃, 5-Cl 3-fluoro-2-pyridinyl Cl CH₃ O 3-Br, 5-Cl3-fluoro-2-pyridinyl Cl CH₃ O 3-Br, 5-Br 3-fluoro-2-pyridinyl Cl CH₃ O3-CH₃, 5-CN 3-fluoro-2-pyridinyl Cl CH₃ O 3-CH₃, 5-Cl3-fluoro-2-pyridinyl Br CH₃ O 3-Br, 5-Cl 3-fluoro-2-pyridinyl Br CH₃ O3-Br, 5-Br 3-fluoro-2-pyridinyl Br CH₃ O 3-CH₃, 5-CN3-fluoro-2-pyridinyl Br CH₃ O 3-CH₃, 5-Cl 3-fluoro-2-pyridinyl CF₃ CH₃ O3-Br, 5-Cl 3-fluoro-2-pyridinyl CF₃ CH₃ O 3-Br, 5-Br3-fluoro-2-pyridinyl CF₃ CH₃ O 3-CH₃, 5-CN 3-fluoro-2-pyridinyl CF₃ CH₃O 3-CH₃, 5-Cl 3-bromo-2-pyridinyl H CH₃ O 3-Br, 5-Cl 3-bromo-2-pyridinylH CH₃ O 3-Br, 5-Br 3-bromo-2-pyridinyl H CH₃ O 3-CH₃, 5-CN3-bromo-2-pyridinyl H CH₃ O 3-CH₃, 5-Cl 3-bromo-2-pyridinyl Cl CH₃ O3-Br, 5-Cl 3-bromo-2-pyridinyl Cl CH₃ O 3-Br, 5-Br 3-bromo-2-pyridinylCl CH₃ O 3-CH₃, 5-CN 3-bromo-2-pyridinyl Cl CH₃ O 3-CH₃, 5-Cl3-bromo-2-pyridinyl Br CH₃ O 3-Br, 5-Cl 3-bromo-2-pyridinyl Br CH₃ O3-Br, 5-Br 3-bromo-2-pyridinyl Br CH₃ O 3-CH₃, 5-CN 3-bromo-2-pyridinylBr CH₃ O 3-CH₃, 5-Cl 3-bromo-2-pyridinyl CF₃ CH₃ O 3-Br, 5-Cl3-bromo-2-pyridinyl CF₃ CH₃ O 3-Br, 5-Br 3-bromo-2-pyridinyl CF₃ CH₃ O3-CH₃, 5-CN 3-bromo-2-pyridinyl CF₃

TABLE 23 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ O 3-CH₃, 5-Cl3-methyl-2-pyridinyl H CH₃ O 3-Br, 5-Cl 3-methyl-2-pyridinyl H CH₃ O3-Br, 5-Br 3-methyl-2-pyridinyl H CH₃ O 3-CH₃, 5-CN 3-methyl-2-pyridinylH CH₃ O 3-CH₃, 5-Cl 3-methyl-2-pyridinyl Cl CH₃ O 3-Br, 5-Cl3-methyl-2-pyridinyl Cl CH₃ O 3-Br, 5-Br 3-methyl-2-pyridinyl Cl CH₃ O3-CH₃, 5-CN 3-methyl-2-pyridinyl Cl CH₃ O 3-CH₃, 5-Cl3-methyl-2-pyridinyl Br CH₃ O 3-Br, 5-Cl 3-methyl-2-pyridinyl Br CH₃ O3-Br, 5-Br 3-methyl-2-pyridinyl Br CH₃ O 3-CH₃, 5-CN3-methyl-2-pyridinyl Br CH₃ O 3-CH₃, 5-Cl 3-methyl-2-pyridinyl CF₃ CH₃ O3-Br, 5-Cl 3-methyl-2-pyridinyl CF₃ CH₃ O 3-Br, 5-Br3-methyl-2-pyridinyl CF₃ CH₃ O 3-CH₃, 5-CN 3-methyl-2-pyridinyl CF₃ CH₃O 3-CH₃, 5-Cl 3-trifluoromethyl-2-pyridinyl H CH₃ O 3-Br, 5-Cl3-trifluoromethyl-2-pyridinyl H CH₃ O 3-Br, 5-Br3-trifluoromethyl-2-pyridinyl H CH₃ O 3-CH₃, 5-CN3-trifluoromethyl-2-pyridinyl H CH₃ O 3-CH₃, 5-Cl3-trifluoromethyl-2-pyridinyl Cl CH₃ O 3-Br, 5-Cl3-trifluoromethyl-2-pyridinyl Cl CH₃ O 3-Br, 5-Br3-trifluoromethyl-2-pyridinyl Cl CH₃ O 3-CH₃, 5-CN3-trifluoromethyl-2-pyridinyl Cl CH₃ O 3-CH₃, 5-Cl3-trifluoromethyl-2-pyridinyl Br CH₃ O 3-Br, 5-Cl3-trifluoromethyl-2-pyridinyl Br CH₃ O 3-Br, 5-Br3-trifluoromethyl-2-pyridinyl Br CH₃ O 3-CH₃, 5-CN3-trifluoromethyl-2-pyridinyl Br CH₃ O 3-CH₃, 5-Cl3-trifluoromethyl-2-pyridinyl CF₃ CH₃ O 3-Br, 5-Cl3-trifluoromethyl-2-pyridinyl CF₃ CH₃ O 3-Br, 5-Br3-trifluoromethyl-2-pyridinyl CF₃ CH₃ O 3-CH₃, 5-CN3-trifluoromethyl-2-pyridinyl CF₃

TABLE 24 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ O 3-CH₃, 5-Cl3-cyano-2-pyridinyl H CH₃ O 3-Br, 5-Cl 3-cyano-2-pyridinyl H CH₃ O 3-Br,5-Br 3-cyano-2-pyridinyl H CH₃ O 3-CH₃, 5-CN 3-cyano-2-pyridinyl H CH₃ O3-CH₃, 5-Cl 3-cyano-2-pyridinyl Cl CH₃ O 3-Br, 5-Cl 3-cyano-2-pyridinylCl CH₃ O 3-Br, 5-Br 3-cyano-2-pyridinyl Cl CH₃ O 3-CH₃, 5-CN3-cyano-2-pyridinyl Cl CH₃ O 3-CH₃, 5-Cl 3-cyano-2-pyridinyl Br CH₃ O3-Br, 5-Cl 3-cyano-2-pyridinyl Br CH₃ O 3-Br, 5-Br 3-cyano-2-pyridinylBr CH₃ O 3-CH₃, 5-CN 3-cyano-2-pyridinyl Br CH₃ O 3-CH₃, 5-Cl3-cyano-2-pyridinyl CF₃ CH₃ O 3-Br, 5-Cl 3-cyano-2-pyridinyl CF₃ CH₃ O3-Br, 5-Br 3-cyano-2-pyridinyl CF₃ CH₃ O 3-CH₃, 5-CN 3-cyano-2-pyridinylCF₃ CH₃ O 3-CH₃, 5-Cl 3-nitro-2-pyridinyl H CH₃ O 3-Br, 5-Cl3-nitro-2-pyridinyl H CH₃ O 3-Br, 5-Br 3-nitro-2-pyridinyl H CH₃ O3-CH₃, 5-CN 3-nitro-2-pyridinyl H CH₃ O 3-CH₃, 5-Cl 3-nitro-2-pyridinylCl CH₃ O 3-Br, 5-Cl 3-nitro-2-pyridinyl Cl CH₃ O 3-Br, 5-Br3-nitro-2-pyridinyl Cl CH₃ O 3-CH₃, 5-CN 3-nitro-2-pyridinyl Cl CH₃ O3-CH₃, 5-Cl 3-nitro-2-pyridinyl Br CH₃ O 3-Br, 5-Cl 3-nitro-2-pyridinylBr CH₃ O 3-Br, 5-Br 3-nitro-2-pyridinyl Br CH₃ O 3-CH₃, 5-CN3-nitro-2-pyridinyl Br CH₃ O 3-CH₃, 5-Cl 3-nitro-2-pyridinyl CF₃ CH₃ O3-Br, 5-Cl 3-nitro-2-pyridinyl CF₃ CH₃ O 3-Br, 5-Br 3-nitro-2-pyridinylCF₃ CH₃ O 3-CH₃, 5-CN 3-nitro-2-pyridinyl CF₃

TABLE 25 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ O 3-CH₃, 5-Cl2-chlorophenyl H CH₃ O 3-Br, 5-Cl 2-chlorophenyl H CH₃ O 3-Br, 5-Br2-chlorophenyl H CH₃ O 3-CH₃, 5-CN 2-chlorophenyl H CH₃ O 3-CH₃, 5-Cl2-chlorophenyl Cl CH₃ O 3-Br, 5-Cl 2-chlorophenyl Cl CH₃ O 3-Br, 5-Br2-chlorophenyl Cl CH₃ O 3-CH₃, 5-CN 2-chlorophenyl Cl CH₃ O 3-CH₃, 5-Cl2-chlorophenyl Br CH₃ O 3-Br, 5-Cl 2-chlorophenyl Br CH₃ O 3-Br, 5-Br2-chlorophenyl Br CH₃ O 3-CH₃, 5-CN 2-chlorophenyl Br CH₃ O 3-CH₃, 5-Cl2-chlorophenyl CF₃ CH₃ O 3-Br, 5-Cl 2-chlorophenyl CF₃ CH₃ O 3-Br, 5-Br2-chlorophenyl CF₃ CH₃ O 3-CH₃, 5-CN 2-chlorophenyl CF₃ CH₃ O 3-CH₃,5-Cl 2,6-dichlorophenyl H CH₃ O 3-Br, 5-Cl 2,6-dichlorophenyl H CH₃ O3-Br, 5-Br 2,6-dichlorophenyl H CH₃ O 3-CH₃, 5-CN 2,6-dichlorophenyl HCH₃ O 3-CH₃, 5-Cl 2,6-dichlorophenyl Cl CH₃ O 3-Br, 5-Cl2,6-dichlorophenyl Cl CH₃ O 3-Br, 5-Br 2,6-dichlorophenyl Cl CH₃ O3-CH₃, 5-CN 2,6-dichlorophenyl Cl CH₃ O 3-CH₃, 5-Cl 2,6-dichlorophenylBr CH₃ O 3-Br, 5-Cl 2,6-dichlorophenyl Br CH₃ O 3-Br, 5-Br2,6-dichlorophenyl Br CH₃ O 3-CH₃, 5-CN 2,6-dichlorophenyl Br CH₃ O3-CH₃, 5-Cl 2,6-dichlorophenyl CF₃ CH₃ O 3-Br, 5-Cl 2,6-dichlorophenylCF₃ CH₃ O 3-Br, 5-Br 2,6-dichlorophenyl CF₃ CH₃ O 3-CH₃, 5-CN2,6-dichlorophenyl CF₃

TABLE 26 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₂CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H CH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl H CH₂CH₃O 3-Br, 5-Br 3-chloro-2-pyridinyl H CH₂CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl H CH₂CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl ClCH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl CH₂CH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl Cl CH₂CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl ClCH₂CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br CH₂CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl Br CH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl BrCH₂CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br CH₂CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ CH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃CH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ CH₂CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃

TABLE 27 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₂CH₂CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H CH₂CH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl HCH₂CH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl H CH₂CH₂CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl H CH₂CH₂CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl ClCH₂CH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl CH₂CH₂CH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl Cl CH₂CH₂CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl ClCH₂CH₂CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br CH₂CH₂CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl Br CH₂CH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl BrCH₂CH₂CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br CH₂CH₂CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ CH₂CH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃CH₂CH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ CH₂CH₂CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃ CH(CH₃)₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl HCH(CH₃)₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl H CH(CH₃)₂ O 3-Br, 5-Br3-chloro-2-pyridinyl H CH(CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl HCH(CH₃)₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl CH(CH₃)₂ O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl CH(CH₃)₂ O 3-Br, 5-Br 3-chloro-2-pyridinyl ClCH(CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl CH(CH₃)₂ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br CH(CH₃)₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl BrCH(CH₃)₂ O 3-Br, 5-Br 3-chloro-2-pyridinyl Br CH(CH₃)₂ O 3-CH₃, 5-CN3-chloro-2-pyridinyl Br CH(CH₃)₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃CH(CH₃)₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ CH(CH₃)₂ O 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ CH(CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

TABLE 28 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) C(CH₃)₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H C(CH₃)₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl HC(CH₃)₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl H C(CH₃)₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl H C(CH₃)₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl ClC(CH₃)₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl C(CH₃)₃ O 3-Br, 5-Br3-chloro-2-pyridinyl Cl C(CH₃)₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl ClC(CH₃)₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br C(CH₃)₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl Br C(CH₃)₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl BrC(CH₃)₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br C(CH₃)₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ C(CH₃)₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃C(CH₃)₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ C(CH₃)₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃ CH₂CH═CH₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl HCH₂CH═CH₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl H CH₂CH═CH₂ O 3-Br, 5-Br3-chloro-2-pyridinyl H CH₂CH═CH₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl HCH₂CH═CH₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl CH₂CH═CH₂ O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl CH₂CH═CH₂ O 3-Br, 5-Br 3-chloro-2-pyridinyl ClCH₂CH═CH₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl CH₂CH═CH₂ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br CH₂CH═CH₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl BrCH₂CH═CH₂ O 3-Br, 5-Br 3-chloro-2-pyridinyl Br CH₂CH═CH₂ O 3-CH₃, 5-CN3-chloro-2-pyridinyl Br CH₂CH═CH₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃CH₂CH═CH₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₂CH═CH₂ O 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ CH₂CH═CH₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinylCF₃

TABLE 29 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₂CCH O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H CH₂CCH O 3-Br, 5-Cl 3-chloro-2-pyridinyl H CH₂CCHO 3-Br, 5-Br 3-chloro-2-pyridinyl H CH₂CCH O 3-CH₃, 5-CN3-chloro-2-pyridinyl H CH₂CCH O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl ClCH₂CCH O 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl CH₂CCH O 3-Br, 5-Br3-chloro-2-pyridinyl Cl CH₂CCH O 3-CH₃, 5-CN 3-chloro-2-pyridinyl ClCH₂CCH O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br CH₂CCH O 3-Br, 5-Cl3-chloro-2-pyridinyl Br CH₂CCH O 3-Br, 5-Br 3-chloro-2-pyridinyl BrCH₂CCH O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br CH₂CCH O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ CH₂CCH O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃CH₂CCH O 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ CH₂CCH O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃ phenyl O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Hphenyl O 3-Br, 5-Cl 3-chloro-2-pyridinyl H phenyl O 3-Br, 5-Br3-chloro-2-pyridinyl H phenyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Hphenyl O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl phenyl O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl phenyl O 3-Br, 5-Br 3-chloro-2-pyridinyl Clphenyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl phenyl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br phenyl O 3-Br, 5-Cl 3-chloro-2-pyridinyl Brphenyl O 3-Br, 5-Br 3-chloro-2-pyridinyl Br phenyl O 3-CH₃, 5-CN3-chloro-2-pyridinyl Br phenyl O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃phenyl O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ phenyl O 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ phenyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

TABLE 30 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ S 3-CH₃, 5-Cl3-chloro-2-pyridinyl H CH₃ S 3-Br, 5-Cl 3-chloro-2-pyridinyl H CH₃ S3-Br, 5-Br 3-chloro-2-pyridinyl H CH₃ S 3-CH₃, 5-CN 3-chloro-2-pyridinylH CH₃ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl CH₃ S 3-Br, 5-Cl3-chloro-2-pyridinyl Cl CH₃ S 3-Br, 5-Br 3-chloro-2-pyridinyl Cl CH₃ S3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl CH₃ S 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br CH₃ S 3-Br, 5-Cl 3-chloro-2-pyridinyl Br CH₃ S3-Br, 5-Br 3-chloro-2-pyridinyl Br CH₃ S 3-CH₃, 5-CN3-chloro-2-pyridinyl Br CH₃ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₃ S3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₃ S 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ CH₃ S 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃CH₂CH₃ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl H CH₂CH₃ S 3-Br, 5-Cl3-chloro-2-pyridinyl H CH₂CH₃ S 3-Br, 5-Br 3-chloro-2-pyridinyl H CH₂CH₃S 3-CH₃, 5-CN 3-chloro-2-pyridinyl H CH₂CH₃ S 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl CH₂CH₃ S 3-Br, 5-Cl 3-chloro-2-pyridinyl ClCH₂CH₃ S 3-Br, 5-Br 3-chloro-2-pyridinyl Cl CH₂CH₃ S 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl CH₂CH₃ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl BrCH₂CH₃ S 3-Br, 5-Cl 3-chloro-2-pyridinyl Br CH₂CH₃ S 3-Br, 5-Br3-chloro-2-pyridinyl Br CH₂CH₃ S 3-CH₃, 5-CN 3-chloro-2-pyridinyl BrCH₂CH₃ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₂CH₃ S 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ CH₂CH₃ S 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃CH₂CH₃ S 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

TABLE 31 R⁶ A³² (R⁴)_(n) R^(13a-1) R^(14a-1) phenyl S 3-CH₃, 5-Cl3-chloro-2-pyridinyl H phenyl S 3-Br, 5-Cl 3-chloro-2-pyridinyl H phenylS 3-Br, 5-Br 3-chloro-2-pyridinyl H phenyl S 3-CH₃, 5-CN3-chloro-2-pyridinyl H phenyl S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Clphenyl S 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl phenyl S 3-Br, 5-Br3-chloro-2-pyridinyl Cl phenyl S 3-CH₃, 5-CN 3-chloro-2-pyridinyl Clphenyl S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br phenyl S 3-Br, 5-Cl3-chloro-2-pyridinyl Br phenyl S 3-Br, 5-Br 3-chloro-2-pyridinyl Brphenyl S 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br phenyl S 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ phenyl S 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃phenyl S 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ phenyl S 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃

A compound represented by the formula (1-R):

wherein R¹, R², R³, (R⁴)_(n) and R^(14a-1) represent combinations shownin Table 32 to Table 39.

TABLE 32 R¹ R² R³ (R⁴)_(n) R^(14a-1) H CH₃ H 3-CH₃, 5-Cl H H CH₃ H 3-Br,5-Cl H H CH₃ H 3-Br, 5-Br H H CH₃ H 3-CH₃, 5-CN H H CH₃ H 3-CH₃, 5-Cl ClH CH₃ H 3-Br, 5-Cl Cl H CH₃ H 3-Br, 5-Br Cl H CH₃ H 3-CH₃, 5-CN Cl H CH₃H 3-CH₃, 5-Cl Br H CH₃ H 3-Br, 5-Cl Br H CH₃ H 3-Br, 5-Br Br H CH₃ H3-CH₃, 5-CN Br H CH₃ H 3-CH₃, 5-Cl CF₃ H CH₃ H 3-Br, 5-Cl CF₃ H CH₃ H3-Br, 5-Br CF₃ H CH₃ H 3-CH₃, 5-CN CF₃ H H CH₃ 3-CH₃, 5-Cl H H H CH₃3-Br, 5-Cl H H H CH₃ 3-Br, 5-Br H H H CH₃ 3-CH₃, 5-CN H H H CH₃ 3-CH₃,5-Cl Cl H H CH₃ 3-Br, 5-Cl Cl H H CH₃ 3-Br, 5-Br Cl H H CH₃ 3-CH₃, 5-CNCl H H CH₃ 3-CH₃, 5-Cl Br H H CH₃ 3-Br, 5-Cl Br H H CH₃ 3-Br, 5-Br Br HH CH₃ 3-CH₃, 5-CN Br H H CH₃ 3-CH₃, 5-Cl CF₃ H H CH₃ 3-Br, 5-Cl CF₃ H HCH₃ 3-Br, 5-Br CF₃ H H CH₃ 3-CH₃, 5-CN CF₃

TABLE 33 R¹ R² R³ (R⁴)_(n) R^(14a-1) H CH₃ CH₃ 3-CH₃, 5-Cl H H CH₃ CH₃3-Br, 5-Cl H H CH₃ CH₃ 3-Br, 5-Br H H CH₃ CH₃ 3-CH₃, 5-CN H H CH₃ CH₃3-CH₃, 5-Cl Cl H CH₃ CH₃ 3-Br, 5-Cl Cl H CH₃ CH₃ 3-Br, 5-Br Cl H CH₃ CH₃3-CH₃, 5-CN Cl H CH₃ CH₃ 3-CH₃, 5-Cl Br H CH₃ CH₃ 3-Br, 5-Cl Br H CH₃CH₃ 3-Br, 5-Br Br H CH₃ CH₃ 3-CH₃, 5-CN Br H CH₃ CH₃ 3-CH₃, 5-Cl CF₃ HCH₃ CH₃ 3-Br, 5-Cl CF₃ H CH₃ CH₃ 3-Br, 5-Br CF₃ H CH₃ CH₃ 3-CH₃, 5-CNCF₃ H H CH₂CH₃ 3-CH₃, 5-Cl H H H CH₂CH₃ 3-Br, 5-Cl H H H CH₂CH₃ 3-Br,5-Br H H H CH₂CH₃ 3-CH₃, 5-CN H H H CH₂CH₃ 3-CH₃, 5-Cl Cl H H CH₂CH₃3-Br, 5-Cl Cl H H CH₂CH₃ 3-Br, 5-Br Cl H H CH₂CH₃ 3-CH₃, 5-CN Cl H HCH₂CH₃ 3-CH₃, 5-Cl Br H H CH₂CH₃ 3-Br, 5-Cl Br H H CH₂CH₃ 3-Br, 5-Br BrH H CH₂CH₃ 3-CH₃, 5-CN Br H H CH₂CH₃ 3-CH₃, 5-Cl CF₃ H H CH₂CH₃ 3-Br,5-Cl CF₃ H H CH₂CH₃ 3-Br, 5-Br CF₃ H H CH₂CH₃ 3-CH₃, 5-CN CF₃

TABLE 34 R¹ R² R³ (R⁴)_(n) R^(14a-1) H H CH(CH₃)₂ 3-CH₃, 5-Cl H H HCH(CH₃)₂ 3-Br, 5-Cl H H H CH(CH₃)₂ 3-Br, 5-Br H H H CH(CH₃)₂ 3-CH₃, 5-CNH H H CH(CH₃)₂ 3-CH₃, 5-Cl Cl H H CH(CH₃)₂ 3-Br, 5-Cl Cl H H CH(CH₃)₂3-Br, 5-Br Cl H H CH(CH₃)₂ 3-CH₃, 5-CN Cl H H CH(CH₃)₂ 3-CH₃, 5-Cl Br HH CH(CH₃)₂ 3-Br, 5-Cl Br H H CH(CH₃)₂ 3-Br, 5-Br Br H H CH(CH₃)₂ 3-CH₃,5-CN Br H H CH(CH₃)₂ 3-CH₃, 5-Cl CF₃ H H CH(CH₃)₂ 3-Br, 5-Cl CF₃ H HCH(CH₃)₂ 3-Br, 5-Br CF₃ H H CH(CH₃)₂ 3-CH₃, 5-CN CF₃ H H C(CH₃)₃ 3-CH₃,5-Cl H H H C(CH₃)₃ 3-Br, 5-Cl H H H C(CH₃)₃ 3-Br, 5-Br H H H C(CH₃)₃3-CH₃, 5-CN H H H C(CH₃)₃ 3-CH₃, 5-Cl Cl H H C(CH₃)₃ 3-Br, 5-Cl Cl H HC(CH₃)₃ 3-Br, 5-Br Cl H H C(CH₃)₃ 3-CH₃, 5-CN Cl H H C(CH₃)₃ 3-CH₃, 5-ClBr H H C(CH₃)₃ 3-Br, 5-Cl Br H H C(CH₃)₃ 3-Br, 5-Br Br H H C(CH₃)₃3-CH₃, 5-CN Br H H C(CH₃)₃ 3-CH₃, 5-Cl CF₃ H H C(CH₃)₃ 3-Br, 5-Cl CF₃ HH C(CH₃)₃ 3-Br, 5-Br CF₃ H H C(CH₃)₃ 3-CH₃, 5-CN CF₃

TABLE 35 R¹ R² R³ (R⁴)_(n) R^(14a-1) H H C(═O)OCH₃ 3-CH₃, 5-Cl H H HC(═O)OCH₃ 3-Br, 5-Cl H H H C(═O)OCH₃ 3-Br, 5-Br H H H C(═O)OCH₃ 3-CH₃,5-CN H H H C(═O)OCH₃ 3-CH₃, 5-Cl Cl H H C(═O)OCH₃ 3-Br, 5-Cl Cl H HC(═O)OCH₃ 3-Br, 5-Br Cl H H C(═O)OCH₃ 3-CH₃, 5-CN Cl H H C(═O)OCH₃3-CH₃, 5-Cl Br H H C(═O)OCH₃ 3-Br, 5-Cl Br H H C(═O)OCH₃ 3-Br, 5-Br Br HH C(═O)OCH₃ 3-CH₃, 5-CN Br H H C(═O)OCH₃ 3-CH₃, 5-Cl CF₃ H H C(═O)OCH₃3-Br, 5-Cl CF₃ H H C(═O)OCH₃ 3-Br, 5-Br CF₃ H H C(═O)OCH₃ 3-CH₃, 5-CNCF₃ H H C(═O)N(CH₃)₂ 3-CH₃, 5-Cl H H H C(═O)N(CH₃)₂ 3-Br, 5-Cl H H HC(═O)N(CH₃)₂ 3-Br, 5-Br H H H C(═O)N(CH₃)₂ 3-CH₃, 5-CN H H HC(═O)N(CH₃)₂ 3-CH₃, 5-Cl Cl H H C(═O)N(CH₃)₂ 3-Br, 5-Cl Cl H HC(═O)N(CH₃)₂ 3-Br, 5-Br Cl H H C(═O)N(CH₃)₂ 3-CH₃, 5-CN Cl H HC(═O)N(CH₃)₂ 3-CH₃, 5-Cl Br H H C(═O)N(CH₃)₂ 3-Br, 5-Cl Br H HC(═O)N(CH₃)₂ 3-Br, 5-Br Br H H C(═O)N(CH₃)₂ 3-CH₃, 5-CN Br H HC(═O)N(CH₃)₂ 3-CH₃, 5-Cl CF₃ H H C(═O)N(CH₃)₂ 3-Br, 5-Cl CF₃ H HC(═O)N(CH₃)₂ 3-Br, 5-Br CF₃ H H C(═O)N(CH₃)₂ 3-CH₃, 5-CN CF₃

TABLE 36 R¹ R² R³ (R⁴)_(n) R^(14a-1) CH₃ CH₃ H 3-CH₃, 5-Cl H CH₃ CH₃ H3-Br, 5-Cl H CH₃ CH₃ H 3-Br, 5-Br H CH₃ CH₃ H 3-CH₃, 5-CN H CH₃ CH₃ H3-CH₃, 5-Cl Cl CH₃ CH₃ H 3-Br, 5-Cl Cl CH₃ CH₃ H 3-Br, 5-Br Cl CH₃ CH₃ H3-CH₃, 5-CN Cl CH₃ CH₃ H 3-CH₃, 5-Cl Br CH₃ CH₃ H 3-Br, 5-Cl Br CH₃ CH₃H 3-Br, 5-Br Br CH₃ CH₃ H 3-CH₃, 5-CN Br CH₃ CH₃ H 3-CH₃, 5-Cl CF₃ CH₃CH₃ H 3-Br, 5-Cl CF₃ CH₃ CH₃ H 3-Br, 5-Br CF₃ CH₃ CH₃ H 3-CH₃, 5-CN CF₃CH₃ H CH₃ 3-CH₃, 5-Cl H CH₃ H CH₃ 3-Br, 5-Cl H CH₃ H CH₃ 3-Br, 5-Br HCH₃ H CH₃ 3-CH₃, 5-CN H CH₃ H CH₃ 3-CH₃, 5-Cl Cl CH₃ H CH₃ 3-Br, 5-Cl ClCH₃ H CH₃ 3-Br, 5-Br Cl CH₃ H CH₃ 3-CH₃, 5-CN Cl CH₃ H CH₃ 3-CH₃, 5-ClBr CH₃ H CH₃ 3-Br, 5-Cl Br CH₃ H CH₃ 3-Br, 5-Br Br CH₃ H CH₃ 3-CH₃, 5-CNBr CH₃ H CH₃ 3-CH₃, 5-Cl CF₃ CH₃ H CH₃ 3-Br, 5-Cl CF₃ CH₃ H CH₃ 3-Br,5-Br CF₃ CH₃ H CH₃ 3-CH₃, 5-CN CF₃

TABLE 37 R¹ R² R³ (R⁴)_(n) R^(14a-1) CH₃ CH₃ CH₃ 3-CH₃, 5-Cl H CH₃ CH₃CH₃ 3-Br, 5-Cl H CH₃ CH₃ CH₃ 3-Br, 5-Br H CH₃ CH₃ CH₃ 3-CH₃, 5-CN H CH₃CH₃ CH₃ 3-CH₃, 5-Cl Cl CH₃ CH₃ CH₃ 3-Br, 5-Cl Cl CH₃ CH₃ CH₃ 3-Br, 5-BrCl CH₃ CH₃ CH₃ 3-CH₃, 5-CN Cl CH₃ CH₃ CH₃ 3-CH₃, 5-Cl Br CH₃ CH₃ CH₃3-Br, 5-Cl Br CH₃ CH₃ CH₃ 3-Br, 5-Br Br CH₃ CH₃ CH₃ 3-CH₃, 5-CN Br CH₃CH₃ CH₃ 3-CH₃, 5-Cl CF₃ CH₃ CH₃ CH₃ 3-Br, 5-Cl CF₃ CH₃ CH₃ CH₃ 3-Br,5-Br CF₃ CH₃ CH₃ CH₃ 3-CH₃, 5-CN CF₃ CH₃ H CH₂CH₃ 3-CH₃, 5-Cl H CH₃ HCH₂CH₃ 3-Br, 5-Cl H CH₃ H CH₂CH₃ 3-Br, 5-Br H CH₃ H CH₂CH₃ 3-CH₃, 5-CN HCH₃ H CH₂CH₃ 3-CH₃, 5-Cl Cl CH₃ H CH₂CH₃ 3-Br, 5-Cl Cl CH₃ H CH₂CH₃3-Br, 5-Br Cl CH₃ H CH₂CH₃ 3-CH₃, 5-CN Cl CH₃ H CH₂CH₃ 3-CH₃, 5-Cl BrCH₃ H CH₂CH₃ 3-Br, 5-Cl Br CH₃ H CH₂CH₃ 3-Br, 5-Br Br CH₃ H CH₂CH₃3-CH₃, 5-CN Br CH₃ H CH₂CH₃ 3-CH₃, 5-Cl CF₃ CH₃ H CH₂CH₃ 3-Br, 5-Cl CF₃CH₃ H CH₂CH₃ 3-Br, 5-Br CF₃ CH₃ H CH₂CH₃ 3-CH₃, 5-CN CF₃

TABLE 38 R¹ R² R³ (R⁴)_(n) R^(14a-1) CH₃ H CH(CH₃)₂ 3-CH₃, 5-Cl H CH₃ HCH(CH₃)₂ 3-Br, 5-Cl H CH₃ H CH(CH₃)₂ 3-Br, 5-Br H CH₃ H CH(CH₃)₂ 3-CH₃,5-CN H CH₃ H CH(CH₃)₂ 3-CH₃, 5-Cl Cl CH₃ H CH(CH₃)₂ 3-Br, 5-Cl Cl CH₃ HCH(CH₃)₂ 3-Br, 5-Br Cl CH₃ H CH(CH₃)₂ 3-CH₃, 5-CN Cl CH₃ H CH(CH₃)₂3-CH₃, 5-Cl Br CH₃ H CH(CH₃)₂ 3-Br, 5-Cl Br CH₃ H CH(CH₃)₂ 3-Br, 5-Br BrCH₃ H CH(CH₃)₂ 3-CH₃, 5-CN Br CH₃ H CH(CH₃)₂ 3-CH₃, 5-Cl CF₃ CH₃ HCH(CH₃)₂ 3-Br, 5-Cl CF₃ CH₃ H CH(CH₃)₂ 3-Br, 5-Br CF₃ CH₃ H CH(CH₃)₂3-CH₃, 5-CN CF₃ CH₃ H C(CH₃)₃ 3-CH₃, 5-Cl H CH₃ H C(CH₃)₃ 3-Br, 5-Cl HCH₃ H C(CH₃)₃ 3-Br, 5-Br H CH₃ H C(CH₃)₃ 3-CH₃, 5-CN H CH₃ H C(CH₃)₃3-CH₃, 5-Cl Cl CH₃ H C(CH₃)₃ 3-Br, 5-Cl Cl CH₃ H C(CH₃)₃ 3-Br, 5-Br ClCH₃ H C(CH₃)₃ 3-CH₃, 5-CN Cl CH₃ H C(CH₃)₃ 3-CH₃, 5-Cl Br CH₃ H C(CH₃)₃3-Br, 5-Cl Br CH₃ H C(CH₃)₃ 3-Br, 5-Br Br CH₃ H C(CH₃)₃ 3-CH₃, 5-CN BrCH₃ H C(CH₃)₃ 3-CH₃, 5-Cl CF₃ CH₃ H C(CH₃)₃ 3-Br, 5-Cl CF₃ CH₃ H C(CH₃)₃3-Br, 5-Br CF₃ CH₃ H C(CH₃)₃ 3-CH₃, 5-CN CF₃

TABLE 39 R¹ R² R³ (R⁴)_(n) R^(14a-1) CH₃ H C(═O)OCH₃ 3-CH₃, 5-Cl H CH₃ HC(═O)OCH₃ 3-Br, 5-Cl H CH₃ H C(═O)OCH₃ 3-Br, 5-Br H CH₃ H C(═O)OCH₃3-CH₃, 5-CN H CH₃ H C(═O)OCH₃ 3-CH₃, 5-Cl Cl CH₃ H C(═O)OCH₃ 3-Br, 5-ClCl CH₃ H C(═O)OCH₃ 3-Br, 5-Br Cl CH₃ H C(═O)OCH₃ 3-CH₃, 5-CN Cl CH₃ HC(═O)OCH₃ 3-CH₃, 5-Cl Br CH₃ H C(═O)OCH₃ 3-Br, 5-Cl Br CH₃ H C(═O)OCH₃3-Br, 5-Br Br CH₃ H C(═O)OCH₃ 3-CH₃, 5-CN Br CH₃ H C(═O)OCH₃ 3-CH₃, 5-ClCF₃ CH₃ H C(═O)OCH₃ 3-Br, 5-Cl CF₃ CH₃ H C(═O)OCH₃ 3-Br, 5-Br CF₃ CH₃ HC(═O)OCH₃ 3-CH₃, 5-CN CF₃ CH₃ H C(═O)N(CH₃)₂ 3-CH₃, 5-Cl H CH₃ HC(═O)N(CH₃)₂ 3-Br, 5-Cl H CH₃ H C(═O)N(CH₃)₂ 3-Br, 5-Br H CH₃ HC(═O)N(CH₃)₂ 3-CH₃, 5-CN H CH₃ H C(═O)N(CH₃)₂ 3-CH₃, 5-Cl Cl CH₃ HC(═O)N(CH₃)₂ 3-Br, 5-Cl Cl CH₃ H C(═O)N(CH₃)₂ 3-Br, 5-Br Cl CH₃ HC(═O)N(CH₃)₂ 3-CH₃, 5-CN Cl CH₃ H C(═O)N(CH₃)₂ 3-CH₃, 5-Cl Br CH₃ HC(═O)N(CH₃)₂ 3-Br, 5-Cl Br CH₃ H C(═O)N(CH₃)₂ 3-Br, 5-Br Br CH₃ HC(═O)N(CH₃)₂ 3-CH₃, 5-CN Br CH₃ H C(═O)N(CH₃)₂ 3-CH₃, 5-Cl CF₃ CH₃ HC(═O)N(CH₃)₂ 3-Br, 5-Cl CF₃ CH₃ H C(═O)N(CH₃)₂ 3-Br, 5-Br CF₃ CH₃ HC(═O)N(CH₃)₂ 3-CH₃, 5-CN CF₃ H CH₃ H 3-Cl, 5-Cl H H CH₃ H 3-Cl, 5-Cl ClH CH₃ H 3-Cl, 5-Cl Br H CH₃ H 3-Cl, 5-Cl CF₃ H H CH₃ 3-Cl, 5-Cl H H HCH₃ 3-Cl, 5-Cl Cl H H CH₃ 3-Cl, 5-Cl Br H H CH₃ 3-Cl, 5-Cl CF₃ H CH₃ CH₃3-Cl, 5-Cl H H CH₃ CH₃ 3-Cl, 5-Cl Cl H CH₃ CH₃ 3-Cl, 5-Cl Br H CH₃ CH₃3-Cl, 5-Cl CF₃ H H CH₂CH₃ 3-Cl, 5-Cl H H H CH₂CH₃ 3-Cl, 5-Cl Cl H HCH₂CH₃ 3-Cl, 5-Cl Br H H CH₂CH₃ 3-Cl, 5-Cl CF₃ H H CH(CH₃)₂ 3-Cl, 5-Cl HH H CH(CH₃)₂ 3-Cl, 5-Cl Cl H H CH(CH₃)₂ 3-Cl, 5-Cl Br H H CH(CH₃)₂ 3-Cl,5-Cl CF₃ H H C(CH₃)₃ 3-Cl, 5-Cl H H H C(CH₃)₃ 3-Cl, 5-Cl Cl H H C(CH₃)₃3-Cl, 5-Cl Br H H C(CH₃)₃ 3-Cl, 5-Cl CF₃ H H C(═O)OCH₃ 3-Cl, 5-Cl H H HC(═O)OCH₃ 3-Cl, 5-Cl Cl H H C(═O)OCH₃ 3-Cl, 5-Cl Br H H C(═O)OCH₃ 3-Cl,5-Cl CF₃ H H C(═O)N(CH₃)₂ 3-Cl, 5-Cl H H H C(═O)N(CH₃)₂ 3-Cl, 5-Cl Cl HH C(═O)N(CH₃)₂ 3-Cl, 5-Cl Br H H C(═O)N(CH₃)₂ 3-Cl, 5-Cl CF₃ CH₃ CH₃ H3-Cl, 5-Cl H CH₃ CH₃ H 3-Cl, 5-Cl Cl CH₃ CH₃ H 3-Cl, 5-Cl Br CH₃ CH₃ H3-Cl, 5-Cl CF₃ CH₃ H CH₃ 3-Cl, 5-Cl H CH₃ H CH₃ 3-Cl, 5-Cl Cl CH₃ H CH₃3-Cl, 5-Cl Br CH₃ H CH₃ 3-Cl, 5-Cl CF₃ CH₃ CH₃ CH₃ 3-Cl, 5-Cl H CH₃ CH₃CH₃ 3-Cl, 5-Cl Cl CH₃ CH₃ CH₃ 3-Cl, 5-Cl Br CH₃ CH₃ CH₃ 3-Cl, 5-Cl CF₃CH₃ H CH₂CH₃ 3-Cl, 5-Cl H CH₃ H CH₂CH₃ 3-Cl, 5-Cl Cl CH₃ H CH₂CH₃ 3-Cl,5-Cl Br CH₃ H CH₂CH₃ 3-Cl, 5-Cl CF₃ CH₃ H CH(CH₃)₂ 3-Cl, 5-Cl H CH₃ HCH(CH₃)₂ 3-Cl, 5-Cl Cl CH₃ H CH(CH₃)₂ 3-Cl, 5-Cl Br CH₃ H CH(CH₃)₂ 3-Cl,5-Cl CF₃ CH₃ H C(CH₃)₃ 3-Cl, 5-Cl H CH₃ H C(CH₃)₃ 3-Cl, 5-Cl Cl CH₃ HC(CH₃)₃ 3-Cl, 5-Cl Br CH₃ H C(CH₃)₃ 3-Cl, 5-Cl CF₃ CH₃ H C(═O)OCH₃ 3-Cl,5-Cl H CH₃ H C(═O)OCH₃ 3-Cl, 5-Cl Cl CH₃ H C(═O)OCH₃ 3-Cl, 5-Cl Br CH₃ HC(═O)OCH₃ 3-Cl, 5-Cl CF₃ CH₃ H C(═O)N(CH₃)₂ 3-Cl, 5-Cl H CH₃ HC(═O)N(CH₃)₂ 3-Cl, 5-Cl Cl CH₃ H C(═O)N(CH₃)₂ 3-Cl, 5-Cl Br CH₃ HC(═O)N(CH₃)₂ 3-Cl, 5-Cl CF₃ H CH₃ CH₂CH₃ 3-CH₃, 5-Cl H H CH₃ CH₂CH₃3-Br, 5-Cl H H CH₃ CH₂CH₃ 3-Br, 5-Br H H CH₃ CH₂CH₃ 3-CH₃, 5-CN H H CH₃CH₂CH₃ 3-Cl, 5-Cl H H CH₃ CH₂CH₃ 3-CH₃, 5-Cl Cl H CH₃ CH₂CH₃ 3-Br, 5-ClCl H CH₃ CH₂CH₃ 3-Br, 5-Br Cl H CH₃ CH₂CH₃ 3-CH₃, 5-CN Cl H CH₃ CH₂CH₃3-Cl, 5-Cl Cl H CH₃ CH₂CH₃ 3-CH₃, 5-Cl Br H CH₃ CH₂CH₃ 3-Br, 5-Cl Br HCH₃ CH₂CH₃ 3-Br, 5-Br Br H CH₃ CH₂CH₃ 3-CH₃, 5-CN Br H CH₃ CH₂CH₃ 3-Cl,5-Cl Br H CH₃ CH₂CH₃ 3-CH₃, 5-Cl CF₃ H CH₃ CH₂CH₃ 3-Br, 5-Cl CF₃ H CH₃CH₂CH₃ 3-Br, 5-Br CF₃ H CH₃ CH₂CH₃ 3-CH₃, 5-CN CF₃ H CH₃ CH₂CH₃ 3-Cl,5-Cl CF₃ H CH₃ CH(CH₃)₂ 3-CH₃, 5-Cl H H CH₃ CH(CH₃)₂ 3-Br, 5-Cl H H CH₃CH(CH₃)₂ 3-Br, 5-Br H H CH₃ CH(CH₃)₂ 3-CH₃, 5-CN H H CH₃ CH(CH₃)₂ 3-Cl,5-Cl H H CH₃ CH(CH₃)₂ 3-CH₃, 5-Cl Cl H CH₃ CH(CH₃)₂ 3-Br, 5-Cl Cl H CH₃CH(CH₃)₂ 3-Br, 5-Br Cl H CH₃ CH(CH₃)₂ 3-CH₃, 5-CN Cl H CH₃ CH(CH₃)₂3-Cl, 5-Cl Cl H CH₃ CH(CH₃)₂ 3-CH₃, 5-Cl Br H CH₃ CH(CH₃)₂ 3-Br, 5-Cl BrH CH₃ CH(CH₃)₂ 3-Br, 5-Br Br H CH₃ CH(CH₃)₂ 3-CH₃, 5-CN Br H CH₃CH(CH₃)₂ 3-Cl, 5-Cl Br H CH₃ CH(CH₃)₂ 3-CH₃, 5-Cl CF₃ H CH₃ CH(CH₃)₂3-Br, 5-Cl CF₃ H CH₃ CH(CH₃)₂ 3-Br, 5-Br CF₃ H CH₃ CH(CH₃)₂ 3-CH₃, 5-CNCF₃ H CH₂CH₃ CH₃ 3-CH₃, 5-Cl H H CH₂CH₃ CH₃ 3-Br, 5-Cl H H CH₂CH₃ CH₃3-Br, 5-Br H H CH₂CH₃ CH₃ 3-CH₃, 5-CN H H CH₂CH₃ CH₃ 3-Cl, 5-Cl H HCH₂CH₃ CH₃ 3-CH₃, 5-Cl Cl H CH₂CH₃ CH₃ 3-Br, 5-Cl Cl H CH₂CH₃ CH₃ 3-Br,5-Br Cl H CH₂CH₃ CH₃ 3-CH₃, 5-CN Cl H CH₂CH₃ CH₃ 3-Cl, 5-Cl Cl H CH₂CH₃CH₃ 3-CH₃, 5-Cl Br H CH₂CH₃ CH₃ 3-Br, 5-Cl Br H CH₂CH₃ CH₃ 3-Br, 5-Br BrH CH₂CH₃ CH₃ 3-CH₃, 5-CN Br H CH₂CH₃ CH₃ 3-Cl, 5-Cl Br H CH₂CH₃ CH₃3-CH₃, 5-Cl CF₃ H CH₂CH₃ CH₃ 3-Br, 5-Cl CF₃ H CH₂CH₃ CH₃ 3-Br, 5-Br CF₃H CH₂CH₃ CH₃ 3-CH₃, 5-CN CF₃ H CH₂CH₃ CH₃ 3-Cl, 5-Cl CF₃ H CH(CH₃)₂ CH₃3-CH₃, 5-Cl H H CH(CH₃)₂ CH₃ 3-Br, 5-Cl H H CH(CH₃)₂ CH₃ 3-Br, 5-Br H HCH(CH₃)₂ CH₃ 3-CH₃, 5-CN H H CH(CH₃)₂ CH₃ 3-Cl, 5-Cl H H CH(CH₃)₂ CH₃3-CH₃, 5-Cl Cl H CH(CH₃)₂ CH₃ 3-Br, 5-Cl Cl H CH(CH₃)₂ CH₃ 3-Br, 5-Br ClH CH(CH₃)₂ CH₃ 3-CH₃, 5-CN Cl H CH(CH₃)₂ CH₃ 3-Cl, 5-Cl Cl H CH(CH₃)₂CH₃ 3-CH₃, 5-Cl Br H CH(CH₃)₂ CH₃ 3-Br, 5-Cl Br H CH(CH₃)₂ CH₃ 3-Br,5-Br Br H CH(CH₃)₂ CH₃ 3-CH₃, 5-CN Br H CH(CH₃)₂ CH₃ 3-Cl, 5-Cl Br HCH(CH₃)₂ CH₃ 3-CH₃, 5-Cl CF₃ H CH(CH₃)₂ CH₃ 3-Br, 5-Cl CF₃ H CH(CH₃)₂CH₃ 3-Br, 5-Br CF₃ H CH(CH₃)₂ CH₃ 3-CH₃, 5-CN CF₃ H CH(CH₃)₂ CH₃ 3-Cl,5-Cl CF₃ H CH₂CH₃ CH₂CH₃ 3-CH₃, 5-Cl H H CH₂CH₃ CH₂CH₃ 3-Br, 5-Cl H HCH₂CH₃ CH₂CH₃ 3-Br, 5-Br H H CH₂CH₃ CH₂CH₃ 3-CH₃, 5-CN H H CH₂CH₃ CH₂CH₃3-Cl, 5-Cl H H CH₂CH₃ CH₂CH₃ 3-CH₃, 5-Cl Cl H CH₂CH₃ CH₂CH₃ 3-Br, 5-ClCl H CH₂CH₃ CH₂CH₃ 3-Br, 5-Br Cl H CH₂CH₃ CH₂CH₃ 3-CH₃, 5-CN Cl H CH₂CH₃CH₂CH₃ 3-Cl, 5-Cl Cl H CH₂CH₃ CH₂CH₃ 3-CH₃, 5-Cl Br H CH₂CH₃ CH₂CH₃3-Br, 5-Cl Br H CH₂CH₃ CH₂CH₃ 3-Br, 5-Br Br H CH₂CH₃ CH₂CH₃ 3-CH₃, 5-CNBr H CH₂CH₃ CH₂CH₃ 3-Cl, 5-Cl Br H CH₂CH₃ CH₂CH₃ 3-CH₃, 5-Cl CF₃ HCH₂CH₃ CH₂CH₃ 3-Br, 5-Cl CF₃ H CH₂CH₃ CH₂CH₃ 3-Br, 5-Br CF₃ H CH₂CH₃CH₂CH₃ 3-CH₃, 5-CN CF₃ H CH₂CH₃ CH₂CH₃ 3-Cl, 5-Cl CF₃

A compound represented by the formula (1-C):

wherein R⁷, A³³, (R⁴)_(n), R^(13a-1) and R^(14a-1) representcombinations shown in Table 40 to Table 41.

TABLE 40 R⁷ A³³ (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl H CH₃ O3-Br, 5-Br 3-chloro-2-pyridinyl H CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinylH CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl Cl CH₃ O3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Br CH₃ O3-Br, 5-Br 3-chloro-2-pyridinyl Br CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl Br CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₃ O3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃CH₂CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl H CH₂CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl H CH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl H CH₂CH₃O 3-CH₃, 5-CN 3-chloro-2-pyridinyl H CH₂CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl CH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl ClCH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl Cl CH₂CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl CH₂CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl BrCH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Br CH₂CH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl Br CH₂CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl BrCH₂CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₂CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ CH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃CH₂CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

TABLE 41 R⁷ A³³ (R⁴)_(n) R^(13a-1) R^(14a-1) phenyl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H phenyl O 3-Br, 5-Cl 3-chloro-2-pyridinyl H phenylO 3-Br, 5-Br 3-chloro-2-pyridinyl H phenyl O 3-CH₃, 5-CN3-chloro-2-pyridinyl H phenyl O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Clphenyl O 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl phenyl O 3-Br, 5-Br3-chloro-2-pyridinyl Cl phenyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Clphenyl O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br phenyl O 3-Br, 5-Cl3-chloro-2-pyridinyl Br phenyl O 3-Br, 5-Br 3-chloro-2-pyridinyl Brphenyl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br phenyl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ phenyl O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃phenyl O 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ phenyl O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃ phenyl S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Hphenyl S 3-Br, 5-Cl 3-chloro-2-pyridinyl H phenyl S 3-Br, 5-Br3-chloro-2-pyridinyl H phenyl S 3-CH₃, 5-CN 3-chloro-2-pyridinyl Hphenyl S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl phenyl S 3-Br, 5-Cl3-chloro-2-pyridinyl Cl phenyl S 3-Br, 5-Br 3-chloro-2-pyridinyl Clphenyl S 3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl phenyl S 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br phenyl S 3-Br, 5-Cl 3-chloro-2-pyridinyl Brphenyl S 3-Br, 5-Br 3-chloro-2-pyridinyl Br phenyl S 3-CH₃, 5-CN3-chloro-2-pyridinyl Br phenyl S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃phenyl S 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ phenyl S 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ phenyl S 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

A compound represented by the formula (1-D):

wherein NR⁸R⁹, A³⁴, (R⁴)_(n), R^(13a-1) and R¹⁴⁻¹ represent combinationsshown in Table 42 to Table 57.

TABLE 42 NR⁸R⁹ A³⁴ (R⁴)_(n) R^(13a-1) R^(14a-1) NH₂ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H NH₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl H NH₂ O3-Br, 5-Br 3-chloro-2-pyridinyl H NH₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinylH NH₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl NH₂ O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl NH₂ O 3-Br, 5-Br 3-chloro-2-pyridinyl Cl NH₂ O3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl NH₂ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br NH₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Br NH₂ O3-Br, 5-Br 3-chloro-2-pyridinyl Br NH₂ O 3-CH₃, 5-CN3-chloro-2-pyridinyl Br NH₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃ NH₂ O3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ NH₂ O 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ NH₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃NHCH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl H NHCH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl H NHCH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl H NHCH₃ O3-CH₃, 5-CN 3-chloro-2-pyridinyl H NHCH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl NHCH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl NHCH₃O 3-Br, 5-Br 3-chloro-2-pyridinyl Cl NHCH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl NHCH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl BrNHCH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Br NHCH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl Br NHCH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl BrNHCH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃ NHCH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ NHCH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃NHCH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

TABLE 43 NR⁸R⁹ A³⁴ (R⁴)_(n) R^(13a-1) R^(14a-1) NHCH₂CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H NHCH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl HNHCH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl H NHCH₂CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl H NHCH₂CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl ClNHCH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl NHCH₂CH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl Cl NHCH₂CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl ClNHCH₂CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br NHCH₂CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl Br NHCH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl BrNHCH₂CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br NHCH₂CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ NHCH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃NHCH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ NHCH₂CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃ NHCH(CH₃)₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl HNHCH(CH₃)₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl H NHCH(CH₃)₂ O 3-Br, 5-Br3-chloro-2-pyridinyl H NHCH(CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl HNHCH(CH₃)₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl NHCH(CH₃)₂ O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl NHCH(CH₃)₂ O 3-Br, 5-Br 3-chloro-2-pyridinyl ClNHCH(CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl NHCH(CH₃)₂ O 3-CH₃,5-Cl 3-chloro-2-pyridinyl Br NHCH(CH₃)₂ O 3-Br, 5-Cl3-chloro-2-pyridinyl Br NHCH(CH₃)₂ O 3-Br, 5-Br 3-chloro-2-pyridinyl BrNHCH(CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br NHCH(CH₃)₂ O 3-CH₃,5-Cl 3-chloro-2-pyridinyl CF₃ NHCH(CH₃)₂ O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ NHCH(CH₃)₂ O 3-Br, 5-Br 3-chloro-2-pyridinylCF₃ NHCH(CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

TABLE 44 NR⁸R⁹ A³⁴ (R⁴)_(n) R^(13a-1) R^(14a-1) NHC(CH₃)₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H NHC(CH₃)₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl HNHC(CH₃)₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl H NHC(CH₃)₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl H NHC(CH₃)₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl ClNHC(CH₃)₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl NHC(CH₃)₃ O 3-Br, 5-Br3-chloro-2-pyridinyl Cl NHC(CH₃)₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl ClNHC(CH₃)₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br NHC(CH₃)₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl Br NHC(CH₃)₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl BrNHC(CH₃)₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br NHC(CH₃)₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ NHC(CH₃)₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃NHC(CH₃)₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ NHC(CH₃)₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃ N(CH₃)₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl HN(CH₃)₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl H N(CH₃)₂ O 3-Br, 5-Br3-chloro-2-pyridinyl H N(CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl HN(CH₃)₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl N(CH₃)₂ O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl N(CH₃)₂ O 3-Br, 5-Br 3-chloro-2-pyridinyl ClN(CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl N(CH₃)₂ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br N(CH₃)₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl BrN(CH₃)₂ O 3-Br, 5-Br 3-chloro-2-pyridinyl Br N(CH₃)₂ O 3-CH₃, 5-CN3-chloro-2-pyridinyl Br N(CH₃)₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃N(CH₃)₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ N(CH₃)₂ O 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ N(CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

TABLE 45 NR⁸R⁹ A³⁴ (R⁴)_(n) R^(13a-1) R^(14a-1) N(CH₂CH₃)₂ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H N(CH₂CH₃)₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl HN(CH₂CH₃)₂ O 3-Br, 5-Br 3-chloro-2-pyridinyl H N(CH₂CH₃)₂ O 3-CH₃, 5-CN3-chloro-2-pyridinyl H N(CH₂CH₃)₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl ClN(CH₂CH₃)₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl N(CH₂CH₃)₂ O 3-Br, 5-Br3-chloro-2-pyridinyl Cl N(CH₂CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl ClN(CH₂CH₃)₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br N(CH₂CH₃)₂ O 3-Br, 5-Cl3-chloro-2-pyridinyl Br N(CH₂CH₃)₂ O 3-Br, 5-Br 3-chloro-2-pyridinyl BrN(CH₂CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br N(CH₂CH₃)₂ O 3-CH₃,5-Cl 3-chloro-2-pyridinyl CF₃ N(CH₂CH₃)₂ O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ N(CH₂CH₃)₂ O 3-Br, 5-Br 3-chloro-2-pyridinylCF₃ N(CH₂CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃ N{CH(CH₃)₂}₂ O3-CH₃, 5-Cl 3-chloro-2-pyridinyl H N{CH (CH₃)₂}₂ O 3-Br, 5-Cl3-chloro-2-pyridinyl H N{CH(CH₃)₂}₂ O 3-Br, 5-Br 3-chloro-2-pyridinyl HN{CH(CH₃)₂}₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl H N{CH(CH₃)₂}₂ O 3-CH₃,5-Cl 3-chloro-2-pyridinyl Cl N{CH(CH₃)₂}₂ O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl N{CH(CH₃)₂}₂ O 3-Br, 5-Br 3-chloro-2-pyridinylCl N{CH(CH₃)₂}₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl N{CH(CH₃)₂}₂ O3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br N{CH(CH₃)₂}₂ O 3-Br, 5-Cl3-chloro-2-pyridinyl Br N{CH(CH₃)₂}₂ O 3-Br, 5-Br 3-chloro-2-pyridinylBr N{CH(CH₃)₂}₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br N{CH(CH₃)₂}₂ O3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃ N{CH(CH₃)₂}₂ O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ N{CH(CH₃)₂}₂ O 3-Br, 5-Br 3-chloro-2-pyridinylCF₃ N{CH (CH₃)₂}₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

TABLE 46 NR⁸R⁹ A³⁴ (R⁴)_(n) R^(13a-1) R^(14a-1) cyclopropylamino O3-CH₃, 5-Cl 3-chloro-2-pyridinyl H cyclopropylamino O 3-Br, 5-Cl3-chloro-2-pyridinyl H cyclopropylamino O 3-Br, 5-Br3-chloro-2-pyridinyl H cyclopropylamino O 3-CH₃, 5-CN3-chloro-2-pyridinyl H cyclopropylamino O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl cyclopropylamino O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl cyclopropylamino O 3-Br, 5-Br3-chloro-2-pyridinyl Cl cyclopropylamino O 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl cyclopropylamino O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br cyclopropylamino O 3-Br, 5-Cl3-chloro-2-pyridinyl Br cyclopropylamino O 3-Br, 5-Br3-chloro-2-pyridinyl Br cyclopropylamino O 3-CH₃, 5-CN3-chloro-2-pyridinyl Br cyclopropylamino O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ cyclopropylamino O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ cyclopropylamino O 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ cyclopropylamino O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃ cyclobutylamino O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H cyclobutylamino O 3-Br, 5-Cl 3-chloro-2-pyridinylH cyclobutylamino O 3-Br, 5-Br 3-chloro-2-pyridinyl H cyclobutylamino O3-CH₃, 5-CN 3-chloro-2-pyridinyl H cyclobutylamino O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl cyclobutylamino O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl cyclobutylamino O 3-Br, 5-Br3-chloro-2-pyridinyl Cl cyclobutylamino O 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl cyclobutylamino O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br cyclobutylamino O 3-Br, 5-Cl3-chloro-2-pyridinyl Br cyclobutylamino O 3-Br, 5-Br3-chloro-2-pyridinyl Br cyclobutylamino O 3-CH₃, 5-CN3-chloro-2-pyridinyl Br cyclobutylamino O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ cyclobutylamino O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ cyclobutylamino O 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ cyclobutylamino O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃

TABLE 47 NR⁸R⁹ A³⁴ (R⁴)_(n) R^(13a-1) R^(14a-1) cyclopentylamino O3-CH₃, 5-Cl 3-chloro-2-pyridinyl H cyclopentylamino O 3-Br, 5-Cl3-chloro-2-pyridinyl H cyclopentylamino O 3-Br, 5-Br3-chloro-2-pyridinyl H cyclopentylamino O 3-CH₃, 5-CN3-chloro-2-pyridinyl H cyclopentylamino O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl cyclopentylamino O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl cyclopentylamino O 3-Br, 5-Br3-chloro-2-pyridinyl Cl cyclopentylamino O 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl cyclopentylamino O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br cyclopentylamino O 3-Br, 5-Cl3-chloro-2-pyridinyl Br cyclopentylamino O 3-Br, 5-Br3-chloro-2-pyridinyl Br cyclopentylamino O 3-CH₃, 5-CN3-chloro-2-pyridinyl Br cyclopentylamino O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ cyclopentylamino O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ cyclopentylamino O 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ cyclopentylamino O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃ cyclohexylamino O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H cyclohexylamino O 3-Br, 5-Cl 3-chloro-2-pyridinylH cyclohexylamino O 3-Br, 5-Br 3-chloro-2-pyridinyl H cyclohexylamino O3-CH₃, 5-CN 3-chloro-2-pyridinyl H cyclohexylamino O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl cyclohexylamino O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl cyclohexylamino O 3-Br, 5-Br3-chloro-2-pyridinyl Cl cyclohexylamino O 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl cyclohexylamino O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br cyclohexylamino O 3-Br, 5-Cl3-chloro-2-pyridinyl Br cyclohexylamino O 3-Br, 5-Br3-chloro-2-pyridinyl Br cyclohexylamino O 3-CH₃, 5-CN3-chloro-2-pyridinyl Br cyclohexylamino O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ cyclohexylamino O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ cyclohexylamino O 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ cyclohexylamino O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃

TABLE 48 NR⁸R⁹ A³⁴ (R⁴)_(n) R^(13a-1) R^(14a-1) anilino O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H anilino O 3-Br, 5-Cl 3-chloro-2-pyridinyl Hanilino O 3-Br, 5-Br 3-chloro-2-pyridinyl H anilino O 3-CH₃, 5-CN3-chloro-2-pyridinyl H anilino O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Clanilino O 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl anilino O 3-Br, 5-Br3-chloro-2-pyridinyl Cl anilino O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Clanilino O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br anilino O 3-Br, 5-Cl3-chloro-2-pyridinyl Br anilino O 3-Br, 5-Br 3-chloro-2-pyridinyl Branilino O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br anilino O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ anilino O 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃anilino O 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ anilino O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃ pyrrolidin-1-yl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H pyrrolidin-1-yl O 3-Br, 5-Cl 3-chloro-2-pyridinylH pyrrolidin-1-yl O 3-Br, 5-Br 3-chloro-2-pyridinyl H pyrrolidin-1-yl O3-CH₃, 5-CN 3-chloro-2-pyridinyl H pyrrolidin-1-yl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl pyrrolidin-1-yl O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl pyrrolidin-1-yl O 3-Br, 5-Br3-chloro-2-pyridinyl Cl pyrrolidin-1-yl O 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl pyrrolidin-1-yl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br pyrrolidin-1-yl O 3-Br, 5-Cl3-chloro-2-pyridinyl Br pyrrolidin-1-yl O 3-Br, 5-Br3-chloro-2-pyridinyl Br pyrrolidin-1-yl O 3-CH₃, 5-CN3-chloro-2-pyridinyl Br pyrrolidin-1-yl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ pyrrolidin-1-yl O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ pyrrolidin-1-yl O 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ pyrrolidin-1-yl O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃

TABLE 49 NR⁸R⁹ A³⁴ (R⁴)_(n) R^(13a-1) R^(14a-1) piperidin-1-yl O 3-CH₃,5-Cl 3-chloro-2-pyridinyl H piperidin-1-yl O 3-Br, 5-Cl3-chloro-2-pyridinyl H piperidin-1-yl O 3-Br, 5-Br 3-chloro-2-pyridinylH piperidin-1-yl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl H piperidin-1-yl O3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl piperidin-1-yl O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl piperidin-1-yl O 3-Br, 5-Br 3-chloro-2-pyridinylCl piperidin-1-yl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl piperidin-1-yl O3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br piperidin-1-yl O 3-Br, 5-Cl3-chloro-2-pyridinyl Br piperidin-1-yl O 3-Br, 5-Br 3-chloro-2-pyridinylBr piperidin-1-yl O 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br piperidin-1-yl O3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃ piperidin-1-yl O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ piperidin-1-yl O 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ piperidin-1-yl O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃ morpholin-4-yl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H morpholin-4-yl O 3-Br, 5-Cl 3-chloro-2-pyridinylH morpholin-4-yl O 3-Br, 5-Br 3-chloro-2-pyridinyl H morpholin-4-yl O3-CH₃, 5-CN 3-chloro-2-pyridinyl H morpholin-4-yl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl morpholin-4-yl O 3-Br, 5-Cl 3-chloro-2-pyridinylCl morpholin-4-yl O 3-Br, 5-Br 3-chloro-2-pyridinyl Cl morpholin-4-yl O3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl morpholin-4-yl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br morpholin-4-yl O 3-Br, 5-Cl 3-chloro-2-pyridinylBr morpholin-4-yl O 3-Br, 5-Br 3-chloro-2-pyridinyl Br morpholin-4-yl O3-CH₃, 5-CN 3-chloro-2-pyridinyl Br morpholin-4-yl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ morpholin-4-yl O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ morpholin-4-yl O 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ morpholin-4-yl O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃

TABLE 50 NR⁸R⁹ A³⁴ (R⁴)_(n) R^(13a-1) R^(14a-1) thiomorpholin-4-yl O3-CH₃, 5-Cl 3-chloro-2-pyridinyl H thiomorpholin-4-yl O 3-Br, 5-Cl3-chloro-2-pyridinyl H thiomorpholin-4-yl O 3-Br, 5-Br3-chloro-2-pyridinyl H thiomorpholin-4-yl O 3-CH₃, 5-CN3-chloro-2-pyridinyl H thiomorpholin-4-yl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl thiomorpholin-4-yl O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl thiomorpholin-4-yl O 3-Br, 5-Br3-chloro-2-pyridinyl Cl thiomorpholin-4-yl O 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl thiomorpholin-4-yl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br thiomorpholin-4-yl O 3-Br, 5-Cl3-chloro-2-pyridinyl Br thiomorpholin-4-yl O 3-Br, 5-Br3-chloro-2-pyridinyl Br thiomorpholin-4-yl O 3-CH₃, 5-CN3-chloro-2-pyridinyl Br thiomorpholin-4-yl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ thiomorpholin-4-yl O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ thiomorpholin-4-yl O 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ thiomorpholin-4-yl O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃ 1-methylpiperazin-4-yl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H 1-methylpiperazin-4-yl O 3-Br, 5-Cl3-chloro-2-pyridinyl H 1-methylpiperazin-4-yl O 3-Br, 5-Br3-chloro-2-pyridinyl H 1-methylpiperazin-4-yl O 3-CH₃, 5-CN3-chloro-2-pyridinyl H 1-methylpiperazin-4-yl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl 1-methylpiperazin-4-yl O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl 1-methylpiperazin-4-yl O 3-Br, 5-Br3-chloro-2-pyridinyl Cl 1-methylpiperazin-4-yl O 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl 1-methylpiperazin-4-yl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br 1-methylpiperazin-4-yl O 3-Br, 5-Cl3-chloro-2-pyridinyl Br 1-methylpiperazin-4-yl O 3-Br, 5-Br3-chloro-2-pyridinyl Br 1-methylpiperazin-4-yl O 3-CH₃, 5-CN3-chloro-2-pyridinyl Br 1-methylpiperazin-4-yl O 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ 1-methylpiperazin-4-yl O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ 1-methylpiperazin-4-yl O 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ 1-methylpiperazin-4-yl O 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃

TABLE 51 NR⁸R⁹ A³⁴ (R⁴)_(n) R^(13a-1) R^(14a-1) NH₂ S 3-CH₃, 5-Cl3-chloro-2-pyridinyl H NH₂ S 3-Br, 5-Cl 3-chloro-2-pyridinyl H NH₂ S3-Br, 5-Br 3-chloro-2-pyridinyl H NH₂ S 3-CH₃, 5-CN 3-chloro-2-pyridinylH NH₂ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl NH₂ S 3-Br, 5-Cl3-chloro-2-pyridinyl Cl NH₂ S 3-Br, 5-Br 3-chloro-2-pyridinyl Cl NH₂ S3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl NH₂ S 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br NH₂ S 3-Br, 5-Cl 3-chloro-2-pyridinyl Br NH₂ S3-Br, 5-Br 3-chloro-2-pyridinyl Br NH₂ S 3-CH₃, 5-CN3-chloro-2-pyridinyl Br NH₂ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃ NH₂ S3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ NH₂ S 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ NH₂ S 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃NHCH₃ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl H NHCH₃ S 3-Br, 5-Cl3-chloro-2-pyridinyl H NHCH₃ S 3-Br, 5-Br 3-chloro-2-pyridinyl H NHCH₃ S3-CH₃, 5-CN 3-chloro-2-pyridinyl H NHCH₃ S 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl NHCH₃ S 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl NHCH₃S 3-Br, 5-Br 3-chloro-2-pyridinyl Cl NHCH₃ S 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl NHCH₃ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl BrNHCH₃ S 3-Br, 5-Cl 3-chloro-2-pyridinyl Br NHCH₃ S 3-Br, 5-Br3-chloro-2-pyridinyl Br NHCH₃ S 3-CH₃, 5-CN 3-chloro-2-pyridinyl BrNHCH₃ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃ NHCH₃ S 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ NHCH₃ S 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃NHCH₃ S 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

TABLE 52 NR⁸R⁹ A³⁴ (R⁴)_(n) R^(13a-1) R^(14a-1) NHCH₂CH₃ S 3-CH₃, 5-Cl3-chloro-2-pyridinyl H NHCH₂CH₃ S 3-Br, 5-Cl 3-chloro-2-pyridinyl HNHCH₂CH₃ S 3-Br, 5-Br 3-chloro-2-pyridinyl H NHCH₂CH₃ S 3-CH₃, 5-CN3-chloro-2-pyridinyl H NHCH₂CH₃ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl ClNHCH₂CH₃ S 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl NHCH₂CH₃ S 3-Br, 5-Br3-chloro-2-pyridinyl Cl NHCH₂CH₃ S 3-CH₃, 5-CN 3-chloro-2-pyridinyl ClNHCH₂CH₃ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br NHCH₂CH₃ S 3-Br, 5-Cl3-chloro-2-pyridinyl Br NHCH₂CH₃ S 3-Br, 5-Br 3-chloro-2-pyridinyl BrNHCH₂CH₃ S 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br NHCH₂CH₃ S 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ NHCH₂CH₃ S 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃NHCH₂CH₃ S 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ NHCH₂CH₃ S 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃ NHCH(CH₃)₂ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl HNHCH(CH₃)₂ S 3-Br, 5-Cl 3-chloro-2-pyridinyl H NHCH(CH₃)₂ S 3-Br, 5-Br3-chloro-2-pyridinyl H NHCH(CH₃)₂ S 3-CH₃, 5-CN 3-chloro-2-pyridinyl HNHCH(CH₃)₂ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl NHCH(CH₃)₂ S 3-Br, 5-Cl3-chloro-2-pyridinyl Cl NHCH(CH₃)₂ S 3-Br, 5-Br 3-chloro-2-pyridinyl ClNHCH(CH₃)₂ S 3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl NHCH(CH₃)₂ S 3-CH₃,5-Cl 3-chloro-2-pyridinyl Br NHCH(CH₃)₂ S 3-Br, 5-Cl3-chloro-2-pyridinyl Br NHCH(CH₃)₂ S 3-Br, 5-Br 3-chloro-2-pyridinyl BrNHCH(CH₃)₂ S 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br NHCH(CH₃)₂ S 3-CH₃,5-Cl 3-chloro-2-pyridinyl CF₃ NHCH(CH₃)₂ S 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ NHCH(CH₃)₂ S 3-Br, 5-Br 3-chloro-2-pyridinylCF₃ NHCH(CH₃)₂ S 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

TABLE 53 NR⁸R⁹ A³⁴ (R⁴)_(n) R^(13a-1) R^(14a-1) NHC(CH₃)₃ S 3-CH₃, 5-Cl3-chloro-2-pyridinyl H NHC(CH₃)₃ S 3-Br, 5-Cl 3-chloro-2-pyridinyl HNHC(CH₃)₃ S 3-Br, 5-Br 3-chloro-2-pyridinyl H NHC(CH₃)₃ S 3-CH₃, 5-CN3-chloro-2-pyridinyl H NHC(CH₃)₃ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl ClNHC(CH₃)₃ S 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl NHC(CH₃)₃ S 3-Br, 5-Br3-chloro-2-pyridinyl Cl NHC(CH₃)₃ S 3-CH₃, 5-CN 3-chloro-2-pyridinyl ClNHC(CH₃)₃ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br NHC(CH₃)₃ S 3-Br, 5-Cl3-chloro-2-pyridinyl Br NHC(CH₃)₃ S 3-Br, 5-Br 3-chloro-2-pyridinyl BrNHC(CH₃)₃ S 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br NHC(CH₃)₃ S 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ NHC(CH₃)₃ S 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃NHC(CH₃)₃ S 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ NHC(CH₃)₃ S 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃ N(CH₃)₂ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl HN(CH₃)₂ S 3-Br, 5-Cl 3-chloro-2-pyridinyl H N(CH₃)₂ S 3-Br, 5-Br3-chloro-2-pyridinyl H N(CH₃)₂ S 3-CH₃, 5-CN 3-chloro-2-pyridinyl HN(CH₃)₂ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl N(CH₃)₂ S 3-Br, 5-Cl3-chloro-2-pyridinyl Cl N(CH₃)₂ S 3-Br, 5-Br 3-chloro-2-pyridinyl ClN(CH₃)₂ S 3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl N(CH₃)₂ S 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br N(CH₃)₂ S 3-Br, 5-Cl 3-chloro-2-pyridinyl BrN(CH₃)₂ S 3-Br, 5-Br 3-chloro-2-pyridinyl Br N(CH₃)₂ S 3-CH₃, 5-CN3-chloro-2-pyridinyl Br N(CH₃)₂ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃N(CH₃)₂ S 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ N(CH₃)₂ S 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ N(CH₃)₂ S 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

TABLE 54 NR⁸R⁹ A³⁴ (R⁴)_(n) R^(13a-1) R^(14a-1) N(CH₂CH₃)₂ S 3-CH₃, 5-Cl3-chloro-2-pyridinyl H N(CH₂CH₃)₂ S 3-Br, 5-Cl 3-chloro-2-pyridinyl HN(CH₂CH₃)₂ S 3-Br, 5-Br 3-chloro-2-pyridinyl H N(CH₂CH₃)₂ S 3-CH₃, 5-CN3-chloro-2-pyridinyl H N(CH₂CH₃)₂ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl ClN(CH₂CH₃)₂ S 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl N(CH₂CH₃)₂ S 3-Br, 5-Br3-chloro-2-pyridinyl Cl N(CH₂CH₃)₂ S 3-CH₃, 5-CN 3-chloro-2-pyridinyl ClN(CH₂CH₃)₂ S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br N(CH₂CH₃)₂ S 3-Br, 5-Cl3-chloro-2-pyridinyl Br N(CH₂CH₃)₂ S 3-Br, 5-Br 3-chloro-2-pyridinyl BrN(CH₂CH₃)₂ S 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br N(CH₂CH₃)₂ S 3-CH₃,5-Cl 3-chloro-2-pyridinyl CF₃ N(CH₂CH₃)₂ S 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ N(CH₂CH₃)₂ S 3-Br, 5-Br 3-chloro-2-pyridinylCF₃ N(CH₂CH₃)₂ S 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃ cyclopropylamino S3-CH₃, 5-Cl 3-chloro-2-pyridinyl H cyclopropylamino S 3-Br, 5-Cl3-chloro-2-pyridinyl H cyclopropylamino S 3-Br, 5-Br3-chloro-2-pyridinyl H cyclopropylamino S 3-CH₃, 5-CN3-chloro-2-pyridinyl H cyclopropylamino S 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl cyclopropylamino S 3-Br, 5-Cl3-chloro-2-pyridinyl Cl cyclopropylamino S 3-Br, 5-Br3-chloro-2-pyridinyl Cl cyclopropylamino S 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl cyclopropylamino S 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br cyclopropylamino S 3-Br, 5-Cl3-chloro-2-pyridinyl Br cyclopropylamino S 3-Br, 5-Br3-chloro-2-pyridinyl Br cyclopropylamino S 3-CH₃, 5-CN3-chloro-2-pyridinyl Br cyclopropylamino S 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ cyclopropylamino S 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ cyclopropylamino S 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ cyclopropylamino S 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃

TABLE 55 NR⁸R⁹ A³⁴ (R⁴)_(n) R^(13a-1) R^(14a-1) cyclobutylamino S 3-CH₃,5-Cl 3-chloro-2-pyridinyl H cyclobutylamino S 3-Br, 5-Cl3-chloro-2-pyridinyl H cyclobutylamino S 3-Br, 5-Br 3-chloro-2-pyridinylH cyclobutylamino S 3-CH₃, 5-CN 3-chloro-2-pyridinyl H cyclobutylamino S3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl cyclobutylamino S 3-Br, 5-Cl3-chloro-2-pyridinyl Cl cyclobutylamino S 3-Br, 5-Br3-chloro-2-pyridinyl Cl cyclobutylamino S 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl cyclobutylamino S 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br cyclobutylamino S 3-Br, 5-Cl3-chloro-2-pyridinyl Br cyclobutylamino S 3-Br, 5-Br3-chloro-2-pyridinyl Br cyclobutylamino S 3-CH₃, 5-CN3-chloro-2-pyridinyl Br cyclobutylamino S 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ cyclobutylamino S 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ cyclobutylamino S 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ cyclobutylamino S 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃ cyclopentylamino S 3-CH₃, 5-Cl3-chloro-2-pyridinyl H cyclopentylamino S 3-Br, 5-Cl3-chloro-2-pyridinyl H cyclopentylamino S 3-Br, 5-Br3-chloro-2-pyridinyl H cyclopentylamino S 3-CH₃, 5-CN3-chloro-2-pyridinyl H cyclopentylamino S 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl cyclopentylamino S 3-Br, 5-Cl3-chloro-2-pyridinyl Cl cyclopentylamino S 3-Br, 5-Br3-chloro-2-pyridinyl Cl cyclopentylamino S 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl cyclopentylamino S 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br cyclopentylamino S 3-Br, 5-Cl3-chloro-2-pyridinyl Br cyclopentylamino S 3-Br, 5-Br3-chloro-2-pyridinyl Br cyclopentylamino S 3-CH₃, 5-CN3-chloro-2-pyridinyl Br cyclopentylamino S 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ cyclopentylamino S 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ cyclopentylamino S 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ cyclopentylamino S 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃

TABLE 56 NR⁸R⁹ A³⁴ (R⁴)_(n) R^(13a-1) R^(14a-1) cyclohexylamino S 3-CH₃,5-Cl 3-chloro-2-pyridinyl H cyclohexylamino S 3-Br, 5-Cl3-chloro-2-pyridinyl H cyclohexylamino S 3-Br, 5-Br 3-chloro-2-pyridinylH cyclohexylamino S 3-CH₃, 5-CN 3-chloro-2-pyridinyl H cyclohexylamino S3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl cyclohexylamino S 3-Br, 5-Cl3-chloro-2-pyridinyl Cl cyclohexylamino S 3-Br, 5-Br3-chloro-2-pyridinyl Cl cyclohexylamino S 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl cyclohexylamino S 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br cyclohexylamino S 3-Br, 5-Cl3-chloro-2-pyridinyl Br cyclohexylamino S 3-Br, 5-Br3-chloro-2-pyridinyl Br cyclohexylamino S 3-CH₃, 5-CN3-chloro-2-pyridinyl Br cyclohexylamino S 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ cyclohexylamino S 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ cyclohexylamino S 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ cyclohexylamino S 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃ anilino S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Hanilino S 3-Br, 5-Cl 3-chloro-2-pyridinyl H anilino S 3-Br, 5-Br3-chloro-2-pyridinyl H anilino S 3-CH₃, 5-CN 3-chloro-2-pyridinyl Hanilino S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl anilino S 3-Br, 5-Cl3-chloro-2-pyridinyl Cl anilino S 3-Br, 5-Br 3-chloro-2-pyridinyl Clanilino S 3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl anilino S 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br anilino S 3-Br, 5-Cl 3-chloro-2-pyridinyl Branilino S 3-Br, 5-Br 3-chloro-2-pyridinyl Br anilino S 3-CH₃, 5-CN3-chloro-2-pyridinyl Br anilino S 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃anilino S 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ anilino S 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ anilino S 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

TABLE 57 NR⁸R⁹ A³⁴ (R⁴)_(n) R^(13a-1) R^(14a-1) morpholin-4-yl S 3-CH₃,5-Cl 3-chloro-2-pyridinyl H morpholin-4-yl S 3-Br, 5-Cl3-chloro-2-pyridinyl H morpholin-4-yl S 3-Br, 5-Br 3-chloro-2-pyridinylH morpholin-4-yl S 3-CH₃, 5-CN 3-chloro-2-pyridinyl H morpholin-4-yl S3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl morpholin-4-yl S 3-Br, 5-Cl3-chloro-2-pyridinyl Cl morpholin-4-yl S 3-Br, 5-Br 3-chloro-2-pyridinylCl morpholin-4-yl S 3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl morpholin-4-yl S3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br morpholin-4-yl S 3-Br, 5-Cl3-chloro-2-pyridinyl Br morpholin-4-yl S 3-Br, 5-Br 3-chloro-2-pyridinylBr morpholin-4-yl S 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br morpholin-4-yl S3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃ morpholin-4-yl S 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ morpholin-4-yl S 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ morpholin-4-yl S 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃

A compound represented by the formula (1-E):

wherein R¹⁰, (R⁴)_(n), R^(13a-1) and R^(14a-1) represent combinationsshown in Table 58 to Table 60.

TABLE 58 R¹⁰ (R⁴)_(n) R^(13a-1) R^(14a-1) CH₃ 3-CH₃, 5-Cl3-chloro-2-pyridinyl H CH₃ 3-Br, 5-Cl 3-chloro-2-pyridinyl H CH₃ 3-Br,5-Br 3-chloro-2-pyridinyl H CH₃ 3-CH₃, 5-CN 3-chloro-2-pyridinyl H CH₃3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl CH₃ 3-Br, 5-Cl 3-chloro-2-pyridinylCl CH₃ 3-Br, 5-Br 3-chloro-2-pyridinyl Cl CH₃ 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl CH₃ 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br CH₃3-Br, 5-Cl 3-chloro-2-pyridinyl Br CH₃ 3-Br, 5-Br 3-chloro-2-pyridinylBr CH₃ 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br CH₃ 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ CH₃ 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₃3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ CH₃ 3-CH₃, 5-CN 3-chloro-2-pyridinylCF₃ CH₂CH₃ 3-CH₃, 5-Cl 3-chloro-2-pyridinyl H CH₂CH₃ 3-Br, 5-Cl3-chloro-2-pyridinyl H CH₂CH₃ 3-Br, 5-Br 3-chloro-2-pyridinyl H CH₂CH₃3-CH₃, 5-CN 3-chloro-2-pyridinyl H CH₂CH₃ 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl CH₂CH₃ 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl CH₂CH₃3-Br, 5-Br 3-chloro-2-pyridinyl Cl CH₂CH₃ 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl CH₂CH₃ 3-CH₃, 5-Cl 3-chloro-2-pyridinyl BrCH₂CH₃ 3-Br, 5-Cl 3-chloro-2-pyridinyl Br CH₂CH₃ 3-Br, 5-Br3-chloro-2-pyridinyl Br CH₂CH₃ 3-CH₃, 5-CN 3-chloro-2-pyridinyl BrCH₂CH₃ 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₂CH₃ 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ CH₂CH₃ 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃CH₂CH₃ 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

TABLE 59 R¹⁰ (R⁴)_(n) R^(13a-1) R^(14a-1) CF₃ 3-CH₃, 5-Cl3-chloro-2-pyridinyl H CF₃ 3-Br, 5-Cl 3-chloro-2-pyridinyl H CF₃ 3-Br,5-Br 3-chloro-2-pyridinyl H CF₃ 3-CH₃, 5-CN 3-chloro-2-pyridinyl H CF₃3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl CF₃ 3-Br, 5-Cl 3-chloro-2-pyridinylCl CF₃ 3-Br, 5-Br 3-chloro-2-pyridinyl Cl CF₃ 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl CF₃ 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br CF₃3-Br, 5-Cl 3-chloro-2-pyridinyl Br CF₃ 3-Br, 5-Br 3-chloro-2-pyridinylBr CF₃ 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br CF₃ 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ CF₃ 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ CF₃3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ CF₃ 3-CH₃, 5-CN 3-chloro-2-pyridinylCF₃ phenyl 3-CH₃, 5-Cl 3-chloro-2-pyridinyl H phenyl 3-Br, 5-Cl3-chloro-2-pyridinyl H phenyl 3-Br, 5-Br 3-chloro-2-pyridinyl H phenyl3-CH₃, 5-CN 3-chloro-2-pyridinyl H phenyl 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl phenyl 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl phenyl3-Br, 5-Br 3-chloro-2-pyridinyl Cl phenyl 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl phenyl 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Brphenyl 3-Br, 5-Cl 3-chloro-2-pyridinyl Br phenyl 3-Br, 5-Br3-chloro-2-pyridinyl Br phenyl 3-CH₃, 5-CN 3-chloro-2-pyridinyl Brphenyl 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃ phenyl 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ phenyl 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃phenyl 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

TABLE 60 R¹⁰ (R⁴)_(n) R^(13a-1) R^(14a-1) 4-methylphenyl 3-CH₃, 5-Cl3-chloro-2-pyridinyl H 4-methylphenyl 3-Br, 5-Cl 3-chloro-2-pyridinyl H4-methylphenyl 3-Br, 5-Br 3-chloro-2-pyridinyl H 4-methylphenyl 3-CH₃,5-CN 3-chloro-2-pyridinyl H 4-methylphenyl 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl 4-methylphenyl 3-Br, 5-Cl 3-chloro-2-pyridinylCl 4-methylphenyl 3-Br, 5-Br 3-chloro-2-pyridinyl Cl 4-methylphenyl3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl 4-methylphenyl 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br 4-methylphenyl 3-Br, 5-Cl 3-chloro-2-pyridinylBr 4-methylphenyl 3-Br, 5-Br 3-chloro-2-pyridinyl Br 4-methylphenyl3-CH₃, 5-CN 3-chloro-2-pyridinyl Br 4-methylphenyl 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ 4-methylphenyl 3-Br, 5-Cl 3-chloro-2-pyridinylCF₃ 4-methylphenyl 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ 4-methylphenyl3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

A compound represented by the formula (1-F):

wherein NR¹¹R¹² (R⁴)_(n), R^(13a-1) and R^(14a-1) represent combinationsshown in Table 61.

TABLE 61 NR¹¹R¹² (R⁴)_(n) R^(13a-1) R^(14a-1) N(CH₃)₂ 3-CH₃, 5-Cl3-chloro-2-pyridinyl H N(CH₃)₂ 3-Br, 5-Cl 3-chloro-2-pyridinyl H N(CH₃)₂3-Br, 5-Br 3-chloro-2-pyridinyl H N(CH₃)₂ 3-CH₃, 5-CN3-chloro-2-pyridinyl H N(CH₃)₂ 3-CH₃, 5-Cl 3-chloro-2-pyridinyl ClN(CH₃)₂ 3-Br, 5-Cl 3-chloro-2-pyridinyl Cl N(CH₃)₂ 3-Br, 5-Br3-chloro-2-pyridinyl Cl N(CH₃) ₂ 3-CH₃, 5-CN 3-chloro-2-pyridinyl ClN(CH₃)₂ 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Br N(CH₃)₂ 3-Br, 5-Cl3-chloro-2-pyridinyl Br N(CH₃) ₂ 3-Br, 5-Br 3-chloro-2-pyridinyl BrN(CH₃)₂ 3-CH₃, 5-CN 3-chloro-2-pyridinyl Br N(CH₃)₂ 3-CH₃, 5-Cl3-chloro-2-pyridinyl CF₃ N(CH₃)₂ 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃N(CH₃)₂ 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃ N(CH₃)₂ 3-CH₃, 5-CN3-chloro-2-pyridinyl CF₃ anilino 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Hanilino 3-Br, 5-Cl 3-chloro-2-pyridinyl H anilino 3-Br, 5-Br3-chloro-2-pyridinyl H anilino 3-CH₃, 5-CN 3-chloro-2-pyridinyl Hanilino 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl anilino 3-Br, 5-Cl3-chloro-2-pyridinyl Cl anilino 3-Br, 5-Br 3-chloro-2-pyridinyl Clanilino 3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl anilino 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br anilino 3-Br, 5-Cl 3-chloro-2-pyridinyl Branilino 3-Br, 5-Br 3-chloro-2-pyridinyl Br anilino 3-CH₃, 5-CN3-chloro-2-pyridinyl Br anilino 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃anilino 3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ anilino 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ anilino 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

A compound represented by the formula (1-G):

wherein R⁵, A³¹, (R⁴)_(n), R^(13a-2) and (R^(14a))_(p) representcombinations shown in Table 62.

TABLE 62 R⁵ A³¹ (R⁴)_(n) R^(13a-2) (R^(14a))_(p) H O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H H O 3-Br, 5-Cl 3-chloro-2-pyridinyl H H O 3-Br,5-Br 3-chloro-2-pyridinyl H H O 3-CH₃, 5-CN 3-chloro-2-pyridinyl H H O3-CH₃, 5-Cl 3-chloro-2-pyridinyl 4-Cl H O 3-Br, 5-Cl3-chloro-2-pyridinyl 4-Cl H O 3-Br, 5-Br 3-chloro-2-pyridinyl 4-Cl H O3-CH₃, 5-CN 3-chloro-2-pyridinyl 4-Cl H O 3-CH₃, 5-Cl3-chloro-2-pyridinyl 4-Br H O 3-Br, 5-Cl 3-chloro-2-pyridinyl 4-Br H O3-Br, 5-Br 3-chloro-2-pyridinyl 4-Br H O 3-CH₃, 5-CN3-chloro-2-pyridinyl 4-Br H O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl 4-CF₃ H O3-Br, 5-Cl 3-chloro-2-pyridinyl 4-CF₃ H O 3-Br, 5-Br3-chloro-2-pyridinyl 4-CF₃ H O 3-CH₃, 5-CN 3-chloro-2-pyridinyl 4-CF₃CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl H CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl H CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl H CH₃ O3-CH₃, 5-CN 3-chloro-2-pyridinyl H CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl 4-Cl CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl 4-Cl CH₃O 3-Br, 5-Br 3-chloro-2-pyridinyl 4-Cl CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl 4-Cl CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl 4-BrCH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl 4-Br CH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl 4-Br CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl 4-BrCH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl 4-CF₃ CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl 4-CF₃ CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl 4-CF₃CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl 4-CF₃

A compound represented by the formula (1-H):

wherein R⁶, A³², (R⁴)_(n), R^(13a-2) and (R^(14a))_(p) representcombinations shown in Table 63 to Table 74.

TABLE 63 R⁶ A³² (R⁴)_(n) R^(13a-2) (R^(14a))_(p) CH₃ O 3-CH₃3-chloro-2-pyridinyl H CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl H CH₃ O3-CH₃, 5-Br 3-chloro-2-pyridinyl H CH₃ O 3-CH₃, 5-I 3-chloro-2-pyridinylH CH₃ O 3-CH₃, 5-CH₃ 3-chloro-2-pyridinyl H CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl H CH₃ O 3-Cl 3-chloro-2-pyridinyl H CH₃ O 3-Cl,5-Cl 3-chloro-2-pyridinyl H CH₃ O 3-Cl, 5-Br 3-chloro-2-pyridinyl H CH₃O 3-Cl, 5-I 3-chloro-2-pyridinyl H CH₃ O 3-Cl, 5-CH₃3-chloro-2-pyridinyl H CH₃ O 3-Cl, 5-CN 3-chloro-2-pyridinyl H CH₃ O3-Br 3-chloro-2-pyridinyl H CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl H CH₃O 3-Br, 5-Br 3-chloro-2-pyridinyl H CH₃ O 3-Br, 5-I 3-chloro-2-pyridinylH CH₃ O 3-Br, 5-CH₃ 3-chloro-2-pyridinyl H CH₃ O 3-Br, 5-CN3-chloro-2-pyridinyl H CH₃ O 3-I 3-chloro-2-pyridinyl H CH₃ O 3-I, 5-Cl3-chloro-2-pyridinyl H CH₃ O 3-I, 5-Br 3-chloro-2-pyridinyl H CH₃ O 3-I,5-I 3-chloro-2-pyridinyl H CH₃ O 3-I, 5-CH₃ 3-chloro-2-pyridinyl H CH₃ O3-I, 5-CN 3-chloro-2-pyridinyl H

TABLE 64 R⁶ A³² (R⁴)_(n) R^(13a-2) (R^(14a))_(p) CH₃ O 3-CH₃3-chloro-2-pyridinyl 4-Cl CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl 4-ClCH₃ O 3-CH₃, 5-Br 3-chloro-2-pyridinyl 4-Cl CH₃ O 3-CH₃, 5-I3-chloro-2-pyridinyl 4-Cl CH₃ O 3-CH₃, 5-CH₃ 3-chloro-2-pyridinyl 4-ClCH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl 4-Cl CH₃ O 3-Cl3-chloro-2-pyridinyl 4-Cl CH₃ O 3-Cl, 5-Cl 3-chloro-2-pyridinyl 4-Cl CH₃O 3-Cl, 5-Br 3-chloro-2-pyridinyl 4-Cl CH₃ O 3-Cl, 5-I3-chloro-2-pyridinyl 4-Cl CH₃ O 3-Cl, 5-CH₃ 3-chloro-2-pyridinyl 4-ClCH₃ O 3-Cl, 5-CN 3-chloro-2-pyridinyl 4-Cl CH₃ O 3-Br3-chloro-2-pyridinyl 4-Cl CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl 4-Cl CH₃O 3-Br, 5-Br 3-chloro-2-pyridinyl 4-Cl CH₃ O 3-Br, 5-I3-chloro-2-pyridinyl 4-Cl CH₃ O 3-Br, 5-CH₃ 3-chloro-2-pyridinyl 4-ClCH₃ O 3-Br, 5-CN 3-chloro-2-pyridinyl 4-Cl CH₃ O 3-I3-chloro-2-pyridinyl 4-Cl CH₃ O 3-I, 5-Cl 3-chloro-2-pyridinyl 4-Cl CH₃O 3-I, 5-Br 3-chloro-2-pyridinyl 4-Cl CH₃ O 3-I, 5-I3-chloro-2-pyridinyl 4-Cl CH₃ O 3-I, 5-CH₃ 3-chloro-2-pyridinyl 4-Cl CH₃O 3-I, 5-CN 3-chloro-2-pyridinyl 4-Cl

TABLE 65 R⁶ A³² (R⁴)_(n) R^(13a-2) (R^(14a))_(p) CH₃ O 3-CH₂CH₃3-chloro-2-pyridinyl 4-Cl CH₃ O 3-CH(CH₃)₂ 3-chloro-2-pyridinyl 4-Cl CH₃O 3-C(CH₃)₃ 3-chloro-2-pyridinyl 4-Cl CH₃ O 3-CF₃ 3-chloro-2-pyridinyl4-Cl CH₃ O 3-OCH₃ 3-chloro-2-pyridinyl 4-Cl CH₃ O 3-phenyl3-chloro-2-pyridinyl 4-Cl CH₃ O 3-CH₂CH₃, 5-Cl 3-chloro-2-pyridinyl 4-ClCH₃ O 3-CH(CH₃)₂, 5-Cl 3-chloro-2-pyridinyl 4-Cl CH₃ O 3-C(CH₃)₃, 5-Cl3-chloro-2-pyridinyl 4-Cl CH₃ O 3-CF₃, 5-Cl 3-chloro-2-pyridinyl 4-ClCH₃ O 3-OCH₃, 5-Cl 3-chloro-2-pyridinyl 4-Cl CH₃ O 3-phenyl, 5-Cl3-chloro-2-pyridinyl 4-Cl CH₃ O 3-CH₃, 4-Cl 3-chloro-2-pyridinyl 4-ClCH₃ O 3-Cl, 4-Cl 3-chloro-2-pyridinyl 4-Cl CH₃ O 3-CH₃, 6-Cl3-chloro-2-pyridinyl 4-Cl CH₃ O 3-Cl, 6-Cl 3-chloro-2-pyridinyl 4-Cl CH₃O 3-CH₃, 4-Cl, 5-Cl 3-chloro-2-pyridinyl 4-Cl CH₃ O 3-Cl, 4-Cl, 5-Cl3-chloro-2-pyridinyl 4-Cl CH₃ O 3-CH₃, 5-Cl, 6-Cl 3-chloro-2-pyridinyl4-Cl CH₃ O 3-Cl, 5-Cl, 6-Cl 3-chloro-2-pyridinyl 4-Cl CH₃ O 3-CH₃, 5-F3-chloro-2-pyridinyl 4-Cl CH₃ O 3-Cl, 5-F 3-chloro-2-pyridinyl 4-Cl CH₃O 3-Br, 5-F 3-chloro-2-pyridinyl 4-Cl CH₃ O 3-I, 5-F3-chloro-2-pyridinyl 4-Cl CH₃ O 3-Me,4,5-CH═CH—CH═CH—3-chloro-2-pyridinyl 4-Cl CH₃ O 3-Cl,4,5-CH═CH—CH═CH—3-chloro-2-pyridinyl 4-Cl CH₃ O 3-Br,4,5-CH═CH—CH═CH—3-chloro-2-pyridinyl 4-Cl CH₃ O 3-I,4,5-CH═CH—CH═CH—3-chloro-2-pyridinyl 4-Cl

TABLE 66 R⁶ A³² (R⁴)_(n) R^(13a-2) (R^(14a))_(p) CH₃ O 3-CH₃3-chloro-2-pyridinyl 4-Br CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl 4-BrCH₃ O 3-CH₃, 5-Br 3-chloro-2-pyridinyl 4-Br CH₃ O 3-CH₃, 5-I3-chloro-2-pyridinyl 4-Br CH₃ O 3-CH₃, 5-CH₃ 3-chloro-2-pyridinyl 4-BrCH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl 4-Br CH₃ O 3-Cl3-chloro-2-pyridinyl 4-Br CH₃ O 3-Cl, 5-Cl 3-chloro-2-pyridinyl 4-Br CH₃O 3-Cl, 5-Br 3-chloro-2-pyridinyl 4-Br CH₃ O 3-Cl, 5-I3-chloro-2-pyridinyl 4-Br CH₃ O 3-Cl, 5-CH₃ 3-chloro-2-pyridinyl 4-BrCH₃ O 3-Cl, 5-CN 3-chloro-2-pyridinyl 4-Br CH₃ O 3-Br3-chloro-2-pyridinyl 4-Br CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl 4-Br CH₃O 3-Br, 5-Br 3-chloro-2-pyridinyl 4-Br CH₃ O 3-Br, 5-I3-chloro-2-pyridinyl 4-Br CH₃ O 3-Br, 5-CH₃ 3-chloro-2-pyridinyl 4-BrCH₃ O 3-Br, 5-CN 3-chloro-2-pyridinyl 4-Br CH₃ O 3-I3-chloro-2-pyridinyl 4-Br CH₃ O 3-I, 5-Cl 3-chloro-2-pyridinyl 4-Br CH₃O 3-I, 5-Br 3-chloro-2-pyridinyl 4-Br CH₃ O 3-I, 5-I3-chloro-2-pyridinyl 4-Br CH₃ O 3-I, 5-CH₃ 3-chloro-2-pyridinyl 4-Br CH₃O 3-I, 5-CN 3-chloro-2-pyridinyl 4-Br

TABLE 67 R⁶ A³² (R⁴)_(n) R^(13a-2) (R^(14a))_(p) CH₃ O 3-CH₂CH₃3-chloro-2-pyridinyl 4-Br CH₃ O 3-CH(CH₃)₂ 3-chloro-2-pyridinyl 4-Br CH₃O 3-C(CH₃)₃ 3-chloro-2-pyridinyl 4-Br CH₃ O 3-CF₃ 3-chloro-2-pyridinyl4-Br CH₃ O 3-OCH₃ 3-chloro-2-pyridinyl 4-Br CH₃ O 3-phenyl3-chloro-2-pyridinyl 4-Br CH₃ O 3-CH₂CH₃, 5-Cl 3-chloro-2-pyridinyl 4-BrCH₃ O 3-CH(CH₃)₂, 5-Cl 3-chloro-2-pyridinyl 4-Br CH₃ O 3-C(CH₃)₃, 5-Cl3-chloro-2-pyridinyl 4-Br CH₃ O 3-CF₃, 5-Cl 3-chloro-2-pyridinyl 4-BrCH₃ O 3-OCH₃, 5-Cl 3-chloro-2-pyridinyl 4-Br CH₃ O 3-phenyl, 5-Cl3-chloro-2-pyridinyl 4-Br CH₃ O 3-CH₃, 4-Cl 3-chloro-2-pyridinyl 4-BrCH₃ O 3-Cl, 4-Cl 3-chloro-2-pyridinyl 4-Br CH₃ O 3-CH₃, 6-Cl3-chloro-2-pyridinyl 4-Br CH₃ O 3-Cl, 6-Cl 3-chloro-2-pyridinyl 4-Br CH₃O 3-CH₃, 4-Cl, 5-Cl 3-chloro-2-pyridinyl 4-Br CH₃ O 3-Cl, 4-Cl, 5-Cl3-chloro-2-pyridinyl 4-Br CH₃ O 3-CH₃, 5-Cl, 6-Cl 3-chloro-2-pyridinyl4-Br CH₃ O 3-Cl, 5-Cl, 6-Cl 3-chloro-2-pyridinyl 4-Br CH₃ O 3-CH₃, 5-F3-chloro-2-pyridinyl 4-Br CH₃ O 3-Cl, 5-F 3-chloro-2-pyridinyl 4-Br CH₃O 3-Br, 5-F 3-chloro-2-pyridinyl 4-Br CH₃ O 3-I, 5-F3-chloro-2-pyridinyl 4-Br CH₃ O 3-Me,4,5-CH═CH—CH═CH—3-chloro-2-pyridinyl 4-Br CH₃ O 3-Cl,4,5-CH═CH—CH═CH—3-chloro-2-pyridinyl 4-Br CH₃ O 3-Br,4,5-CH═CH—CH═CH—3-chloro-2-pyridinyl 4-Br CH₃ O 3-I,4,5-CH═CH—CH═CH—3-chloro-2-pyridinyl 4-Br

TABLE 68 R⁶ A³² (R⁴)_(n) R^(13a-2) (R^(14a))_(p) CH₃ O 3-CH₃3-chloro-2-pyridinyl 4-CF₃ CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl 4-CF₃CH₃ O 3-CH₃, 5-Br 3-chloro-2-pyridinyl 4-CF₃ CH₃ O 3-CH₃, 5-I3-chloro-2-pyridinyl 4-CF₃ CH₃ O 3-CH₃, 5-CH₃ 3-chloro-2-pyridinyl 4-CF₃CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl 4-CF₃ CH₃ O 3-Cl3-chloro-2-pyridinyl 4-CF₃ CH₃ O 3-Cl, 5-Cl 3-chloro-2-pyridinyl 4-CF₃CH₃ O 3-Cl, 5-Br 3-chloro-2-pyridinyl 4-CF₃ CH₃ O 3-Cl, 5-I3-chloro-2-pyridinyl 4-CF₃ CH₃ O 3-Cl, 5-CH₃ 3-chloro-2-pyridinyl 4-CF₃CH₃ O 3-Cl, 5-CN 3-chloro-2-pyridinyl 4-CF₃ CH₃ O 3-Br3-chloro-2-pyridinyl 4-CF₃ CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl 4-CF₃CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl 4-CF₃ CH₃ O 3-Br, 5-I3-chloro-2-pyridinyl 4-CF₃ CH₃ O 3-Br, 5-CH₃ 3-chloro-2-pyridinyl 4-CF₃CH₃ O 3-Br, 5-CN 3-chloro-2-pyridinyl 4-CF₃ CH₃ O 3-I3-chloro-2-pyridinyl 4-CF₃ CH₃ O 3-I, 5-Cl 3-chloro-2-pyridinyl 4-CF₃CH₃ O 3-I, 5-Br 3-chloro-2-pyridinyl 4-CF₃ CH₃ O 3-I, 5-I3-chloro-2-pyridinyl 4-CF₃ CH₃ O 3-I, 5-CH₃ 3-chloro-2-pyridinyl 4-CF₃CH₃ O 3-I, 5-CN 3-chloro-2-pyridinyl 4-CF₃

TABLE 69 R⁶ A³² (R⁴)_(n) R^(13a-2) (R^(14a))_(p) CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl 4-F CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl 4-F CH₃ O3-Br, 5-Br 3-chloro-2-pyridinyl 4-F CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl 4-F CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl 4-I CH₃O 3-Br, 5-Cl 3-chloro-2-pyridinyl 4-I CH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl 4-I CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl 4-I CH₃O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl 4-CH₃ CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl 4-CH₃ CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl 4-CH₃CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl 4-CH₃ CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl 5-Cl CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl 5-Cl CH₃O 3-Br, 5-Br 3-chloro-2-pyridinyl 5-Cl CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl 5-Cl CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl 5-BrCH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl 5-Br CH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl 5-Br CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl 5-BrCH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl 5-CF₃ CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl 5-CF₃ CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl 5-CF₃CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl 5-CF₃ CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl 4,5-Cl₂ CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl4,5-Cl₂ CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl 4,5-Cl₂ CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl 4,5-Cl₂ CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl4,5-Br₂ CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl 4,5-Br₂ CH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl 4,5-Br₂ CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl4,5-Br₂

TABLE 70 R⁶ A³² (R⁴)_(n) R^(13a-2) (R^(14a))_(p) CH₃ O 3-CH₃, 5-Cl3-fluoro-2-pyridinyl H CH₃ O 3-Br, 5-Cl 3-fluoro-2-pyridinyl H CH₃ O3-Br, 5-Br 3-fluoro-2-pyridinyl H CH₃ O 3-CH₃, 5-CN 3-fluoro-2-pyridinylH CH₃ O 3-CH₃, 5-Cl 3-fluoro-2-pyridinyl 4-Cl CH₃ O 3-Br, 5-Cl3-fluoro-2-pyridinyl 4-Cl CH₃ O 3-Br, 5-Br 3-fluoro-2-pyridinyl 4-Cl CH₃O 3-CH₃, 5-CN 3-fluoro-2-pyridinyl 4-Cl CH₃ O 3-CH₃, 5-Cl3-fluoro-2-pyridinyl 4-Br CH₃ O 3-Br, 5-Cl 3-fluoro-2-pyridinyl 4-Br CH₃O 3-Br, 5-Br 3-fluoro-2-pyridinyl 4-Br CH₃ O 3-CH₃, 5-CN3-fluoro-2-pyridinyl 4-Br CH₃ O 3-CH₃, 5-Cl 3-fluoro-2-pyridinyl 4-CF₃CH₃ O 3-Br, 5-Cl 3-fluoro-2-pyridinyl 4-CF₃ CH₃ O 3-Br, 5-Br3-fluoro-2-pyridinyl 4-CF₃ CH₃ O 3-CH₃, 5-CN 3-fluoro-2-pyridinyl 4-CF₃CH₃ O 3-CH₃, 5-Cl 3-bromo-2-pyridinyl H CH₃ O 3-Br, 5-Cl3-bromo-2-pyridinyl H CH₃ O 3-Br, 5-Br 3-bromo-2-pyridinyl H CH₃ O3-CH₃, 5-CN 3-bromo-2-pyridinyl H CH₃ O 3-CH₃, 5-Cl 3-bromo-2-pyridinyl4-Cl CH₃ O 3-Br, 5-Cl 3-bromo-2-pyridinyl 4-Cl CH₃ O 3-Br, 5-Br3-bromo-2-pyridinyl 4-Cl CH₃ O 3-CH₃, 5-CN 3-bromo-2-pyridinyl 4-Cl CH₃O 3-CH₃, 5-Cl 3-bromo-2-pyridinyl 4-Br CH₃ O 3-Br, 5-Cl3-bromo-2-pyridinyl 4-Br CH₃ O 3-Br, 5-Br 3-bromo-2-pyridinyl 4-Br CH₃ O3-CH₃, 5-CN 3-bromo-2-pyridinyl 4-Br CH₃ O 3-CH₃, 5-Cl3-bromo-2-pyridinyl 4-CF₃ CH₃ O 3-Br, 5-Cl 3-bromo-2-pyridinyl 4-CF₃ CH₃O 3-Br, 5-Br 3-bromo-2-pyridinyl 4-CF₃ CH₃ O 3-CH₃, 5-CN3-bromo-2-pyridinyl 4-CF₃

TABLE 71 R⁶ A³² (R⁴)_(n) R^(13a-2) (R^(14a))_(p) CH₃ O 3-CH₃, 5-Cl3-methyl-2-pyridinyl H CH₃ O 3-Br, 5-Cl 3-methyl-2-pyridinyl H CH₃ O3-Br, 5-Br 3-methyl-2-pyridinyl H CH₃ O 3-CH₃, 5-CN 3-methyl-2-pyridinylH CH₃ O 3-CH₃, 5-Cl 3-methyl-2-pyridinyl 4-Cl CH₃ O 3-Br, 5-Cl3-methyl-2-pyridinyl 4-Cl CH₃ O 3-Br, 5-Br 3-methyl-2-pyridinyl 4-Cl CH₃O 3-CH₃, 5-CN 3-methyl-2-pyridinyl 4-Cl CH₃ O 3-CH₃, 5-Cl3-methyl-2-pyridinyl 4-Br CH₃ O 3-Br, 5-Cl 3-methyl-2-pyridinyl 4-Br CH₃O 3-Br, 5-Br 3-methyl-2-pyridinyl 4-Br CH₃ O 3-CH₃, 5-CN3-methyl-2-pyridinyl 4-Br CH₃ O 3-CH₃, 5-Cl 3-methyl-2-pyridinyl 4-CF₃CH₃ O 3-Br, 5-Cl 3-methyl-2-pyridinyl 4-CF₃ CH₃ O 3-Br, 5-Br3-methyl-2-pyridinyl 4-CF₃ CH₃ O 3-CH₃, 5-CN 3-methyl-2-pyridinyl 4-CF₃CH₃ O 3-CH₃, 5-Cl 3-trifluoromethyl-2-pyridinyl H CH₃ O 3-Br, 5-Cl3-trifluoromethyl-2-pyridinyl H CH₃ O 3-Br, 5-Br3-trifluoromethyl-2-pyridinyl H CH₃ O 3-CH₃, 5-CN3-trifluoromethyl-2-pyridinyl H CH₃ O 3-CH₃, 5-Cl3-trifluoromethyl-2-pyridinyl 4-Cl CH₃ O 3-Br, 5-Cl3-trifluoromethyl-2-pyridinyl 4-Cl CH₃ O 3-Br, 5-Br3-trifluoromethyl-2-pyridinyl 4-Cl CH₃ O 3-CH₃, 5-CN3-trifluoromethyl-2-pyridinyl 4-Cl CH₃ O 3-CH₃, 5-Cl3-trifluoromethyl-2-pyridinyl 4-Br CH₃ O 3-Br, 5-Cl3-trifluoromethyl-2-pyridinyl 4-Br CH₃ O 3-Br, 5-Br3-trifluoromethyl-2-pyridinyl 4-Br CH₃ O 3-CH₃, 5-CN3-trifluoromethyl-2-pyridinyl 4-Br CH₃ O 3-CH₃, 5-Cl3-trifluoromethyl-2-pyridinyl 4-CF₃ CH₃ O 3-Br, 5-Cl3-trifluoromethyl-2-pyridinyl 4-CF₃ CH₃ O 3-Br, 5-Br3-trifluoromethyl-2-pyridinyl 4-CF₃ CH₃ O 3-CH₃, 5-CN3-trifluoromethyl-2-pyridinyl 4-CF₃

TABLE 72 R⁶ A³² (R⁴)_(n) R^(13a-2) (R^(14a))_(p) CH₃ O 3-CH₃, 5-Cl3-cyano-2-pyridinyl H CH₃ O 3-Br, 5-Cl 3-cyano-2-pyridinyl H CH₃ O 3-Br,5-Br 3-cyano-2-pyridinyl H CH₃ O 3-CH₃, 5-CN 3-cyano-2-pyridinyl H CH₃ O3-CH₃, 5-Cl 3-cyano-2-pyridinyl 4-Cl CH₃ O 3-Br, 5-Cl3-cyano-2-pyridinyl 4-Cl CH₃ O 3-Br, 5-Br 3-cyano-2-pyridinyl 4-Cl CH₃ O3-CH₃, 5-CN 3-cyano-2-pyridinyl 4-Cl CH₃ O 3-CH₃, 5-Cl3-cyano-2-pyridinyl 4-Br CH₃ O 3-Br, 5-Cl 3-cyano-2-pyridinyl 4-Br CH₃ O3-Br, 5-Br 3-cyano-2-pyridinyl 4-Br CH₃ O 3-CH₃, 5-CN3-cyano-2-pyridinyl 4-Br CH₃ O 3-CH₃, 5-Cl 3-cyano-2-pyridinyl 4-CF₃ CH₃O 3-Br, 5-Cl 3-cyano-2-pyridinyl 4-CF₃ CH₃ O 3-Br, 5-Br3-cyano-2-pyridinyl 4-CF₃ CH₃ O 3-CH₃, 5-CN 3-cyano-2-pyridinyl 4-CF₃CH₃ O 3-CH₃, 5-Cl 3-nitro-2-pyridinyl H CH₃ O 3-Br, 5-Cl3-nitro-2-pyridinyl H CH₃ O 3-Br, 5-Br 3-nitro-2-pyridinyl H CH₃ O3-CH₃, 5-CN 3-nitro-2-pyridinyl H CH₃ O 3-CH₃, 5-Cl 3-nitro-2-pyridinyl4-Cl CH₃ O 3-Br, 5-Cl 3-nitro-2-pyridinyl 4-Cl CH₃ O 3-Br, 5-Br3-nitro-2-pyridinyl 4-Cl CH₃ O 3-CH₃, 5-CN 3-nitro-2-pyridinyl 4-Cl CH₃O 3-CH₃, 5-Cl 3-nitro-2-pyridinyl 4-Br CH₃ O 3-Br, 5-Cl3-nitro-2-pyridinyl 4-Br CH₃ O 3-Br, 5-Br 3-nitro-2-pyridinyl 4-Br CH₃ O3-CH₃, 5-CN 3-nitro-2-pyridinyl 4-Br CH₃ O 3-CH₃, 5-Cl3-nitro-2-pyridinyl 4-CF₃ CH₃ O 3-Br, 5-Cl 3-nitro-2-pyridinyl 4-CF₃ CH₃O 3-Br, 5-Br 3-nitro-2-pyridinyl 4-CF₃ CH₃ O 3-CH₃, 5-CN3-nitro-2-pyridinyl 4-CF₃

TABLE 73 R⁶ A³² (R⁴)_(n) R^(13a-2) (R^(14a))_(p) CH₃ O 3-CH₃, 5-Cl2-chlorophenyl H CH₃ O 3-Br, 5-Cl 2-chlorophenyl H CH₃ O 3-Br, 5-Br2-chlorophenyl H CH₃ O 3-CH₃, 5-CN 2-chlorophenyl H CH₃ O 3-CH₃, 5-Cl2-chlorophenyl 4-Cl CH₃ O 3-Br, 5-Cl 2-chlorophenyl 4-Cl CH₃ O 3-Br,5-Br 2-chlorophenyl 4-Cl CH₃ O 3-CH₃, 5-CN 2-chlorophenyl 4-Cl CH₃ O3-CH₃, 5-Cl 2-chlorophenyl 4-Br CH₃ O 3-Br, 5-Cl 2-chlorophenyl 4-Br CH₃O 3-Br, 5-Br 2-chlorophenyl 4-Br CH₃ O 3-CH₃, 5-CN 2-chlorophenyl 4-BrCH₃ O 3-CH₃, 5-Cl 2-chlorophenyl 4-CF₃ CH₃ O 3-Br, 5-Cl 2-chlorophenyl4-CF₃ CH₃ O 3-Br, 5-Br 2-chlorophenyl 4-CF₃ CH₃ O 3-CH₃, 5-CN2-chlorophenyl 4-CF₃ CH₃ O 3-CH₃, 5-Cl 2,6-dichlorophenyl H CH₃ O 3-Br,5-Cl 2,6-dichlorophenyl H CH₃ O 3-Br, 5-Br 2,6-dichlorophenyl H CH₃ O3-CH₃, 5-CN 2,6-dichlorophenyl H CH₃ O 3-CH₃, 5-Cl 2,6-dichlorophenyl4-Cl CH₃ O 3-Br, 5-Cl 2,6-dichlorophenyl 4-Cl CH₃ O 3-Br, 5-Br2,6-dichlorophenyl 4-Cl CH₃ O 3-CH₃, 5-CN 2,6-dichlorophenyl 4-Cl CH₃ O3-CH₃, 5-Cl 2,6-dichlorophenyl 4-Br CH₃ O 3-Br, 5-Cl 2,6-dichlorophenyl4-Br CH₃ O 3-Br, 5-Br 2,6-dichlorophenyl 4-Br CH₃ O 3-CH₃, 5-CN2,6-dichlorophenyl 4-Br CH₃ O 3-CH₃, 5-Cl 2,6-dichlorophenyl 4-CF₃ CH₃ O3-Br, 5-Cl 2,6-dichlorophenyl 4-CF₃ CH₃ O 3-Br, 5-Br 2,6-dichlorophenyl4-CF₃ CH₃ O 3-CH₃, 5-CN 2,6-dichlorophenyl 4-CF₃

TABLE 74 R⁶ A³² (R⁴)_(n) R^(13a-2) (R^(14a))_(p) CH₂CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H CH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl H CH₂CH₃O 3-Br, 5-Br 3-chloro-2-pyridinyl H CH₂CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl H CH₂CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl 4-ClCH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl 4-Cl CH₂CH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl 4-Cl CH₂CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl 4-ClCH₂CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl 4-Br CH₂CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl 4-Br CH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl 4-BrCH₂CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl 4-Br CH₂CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl 4-CF₃ CH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl4-CF₃ CH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl 4-CF₃ CH₂CH₃ O 3-CH₃,5-CN 3-chloro-2-pyridinyl 4-CF₃ CH₃ O 3-Cl, 5-Cl 3-chloro-2-pyridinyl4-F CH₃ O 3-Cl, 5-Cl 3-chloro-2-pyridinyl 4-I CH₃ O 3-Cl, 5-Cl3-chloro-2-pyridinyl 4-CH₃ CH₃ O 3-Cl, 5-Cl 3-chloro-2-pyridinyl 5-ClCH₃ O 3-Cl, 5-Cl 3-chloro-2-pyridinyl 5-Br CH₃ O 3-Cl, 5-Cl3-chloro-2-pyridinyl 5-CF₃ CH₃ O 3-Cl, 5-Cl 3-chloro-2-pyridinyl 4,5-Cl₂CH₃ O 3-Cl, 5-Cl 3-chloro-2-pyridinyl 4,5-Br₂ CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl 4-Cl, 5-Br CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl4-Cl, 5-Br CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl 4-Cl, 5-Br CH₃ O 3-CH₃,5-CN 3-chloro-2-pyridinyl 4-Cl, 5-Br CH₃ O 3-Cl, 5-Cl3-chloro-2-pyridinyl 4-Cl, 5-Br CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl4-Br, 5-Cl CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl 4-Br, 5-Cl CH₃ O 3-Br,5-Br 3-chloro-2-pyridinyl 4-Br, 5-Cl CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl 4-Br, 5-Cl CH₃ O 3-Cl, 5-Cl 3-chloro-2-pyridinyl4-Br, 5-Cl

A compound represented by the formula (1-S):

wherein R¹, R², R³, (R⁴)_(n) and (R^(14a))_(p) represent combinationsshown in Table 75 to Table 82.

TABLE 75 R¹ R² R³ (R⁴)_(n) (R^(14a))_(p) H CH₃ H 3-CH₃, 5-Cl H H CH₃ H3-Br, 5-Cl H H CH₃ H 3-Br, 5-Br H H CH₃ H 3-CH₃, 5-CN H H CH₃ H 3-CH₃,5-Cl 4-Cl H CH₃ H 3-Br, 5-Cl 4-Cl H CH₃ H 3-Br, 5-Br 4-Cl H CH₃ H 3-CH₃,5-CN 4-Cl H CH₃ H 3-CH₃, 5-Cl 4-Br H CH₃ H 3-Br, 5-Cl 4-Br H CH₃ H 3-Br,5-Br 4-Br H CH₃ H 3-CH₃, 5-CN 4-Br H CH₃ H 3-CH₃, 5-Cl 4-CF₃ H CH₃ H3-Br, 5-Cl 4-CF₃ H CH₃ H 3-Br, 5-Br 4-CF₃ H CH₃ H 3-CH₃, 5-CN 4-CF₃ H HCH₃ 3-CH₃, 5-Cl H H H CH₃ 3-Br, 5-Cl H H H CH₃ 3-Br, 5-Br H H H CH₃3-CH₃, 5-CN H H H CH₃ 3-CH₃, 5-Cl 4-Cl H H CH₃ 3-Br, 5-Cl 4-Cl H H CH₃3-Br, 5-Br 4-Cl H H CH₃ 3-CH₃, 5-CN 4-Cl H H CH₃ 3-CH₃, 5-Cl 4-Br H HCH₃ 3-Br, 5-Cl 4-Br H H CH₃ 3-Br, 5-Br 4-Br H H CH₃ 3-CH₃, 5-CN 4-Br H HCH₃ 3-CH₃, 5-Cl 4-CF₃ H H CH₃ 3-Br, 5-Cl 4-CF₃ H H CH₃ 3-Br, 5-Br 4-CF₃H H CH₃ 3-CH₃, 5-CN 4-CF₃

TABLE 76 R¹ R² R³ (R⁴)_(n) (R^(14a))_(p) H CH₃ CH₃ 3-CH₃, 5-Cl H H CH₃CH₃ 3-Br, 5-Cl H H CH₃ CH₃ 3-Br, 5-Br H H CH₃ CH₃ 3-CH₃, 5-CN H H CH₃CH₃ 3-CH₃, 5-Cl 4-Cl H CH₃ CH₃ 3-Br, 5-Cl 4-Cl H CH₃ CH₃ 3-Br, 5-Br 4-ClH CH₃ CH₃ 3-CH₃, 5-CN 4-Cl H CH₃ CH₃ 3-CH₃, 5-Cl 4-Br H CH₃ CH₃ 3-Br,5-Cl 4-Br H CH₃ CH₃ 3-Br, 5-Br 4-Br H CH₃ CH₃ 3-CH₃, 5-CN 4-Br H CH₃ CH₃3-CH₃, 5-Cl 4-CF₃ H CH₃ CH₃ 3-Br, 5-Cl 4-CF₃ H CH₃ CH₃ 3-Br, 5-Br 4-CF₃H CH₃ CH₃ 3-CH₃, 5-CN 4-CF₃ H H CH₂CH₃ 3-CH₃, 5-Cl H H H CH₂CH₃ 3-Br,5-Cl H H H CH₂CH₃ 3-Br, 5-Br H H H CH₂CH₃ 3-CH₃, 5-CN H H H CH₂CH₃3-CH₃, 5-Cl 4-Cl H H CH₂CH₃ 3-Br, 5-Cl 4-Cl H H CH₂CH₃ 3-Br, 5-Br 4-Cl HH CH₂CH₃ 3-CH₃, 5-CN 4-Cl H H CH₂CH₃ 3-CH₃, 5-Cl 4-Br H H CH₂CH₃ 3-Br,5-Cl 4-Br H H CH₂CH₃ 3-Br, 5-Br 4-Br H H CH₂CH₃ 3-CH₃, 5-CN 4-Br H HCH₂CH₃ 3-CH₃, 5-Cl 4-CF₃ H H CH₂CH₃ 3-Br, 5-Cl 4-CF₃ H H CH₂CH₃ 3-Br,5-Br 4-CF₃ H H CH₂CH₃ 3-CH₃, 5-CN 4-CF₃

TABLE 77 R¹ R² R³ (R⁴)_(n) (R^(14a))_(p) H H CH(CH₃)₂ 3-CH₃, 5-Cl H H HCH(CH₃)₂ 3-Br, 5-Cl H H H CH(CH₃)₂ 3-Br, 5-Br H H H CH(CH₃)₂ 3-CH₃, 5-CNH H H CH(CH₃)₂ 3-CH₃, 5-Cl 4-Cl H H CH(CH₃)₂ 3-Br, 5-Cl 4-Cl H HCH(CH₃)₂ 3-Br, 5-Br 4-Cl H H CH(CH₃)₂ 3-CH₃, 5-CN 4-Cl H H CH(CH₃)₂3-CH₃, 5-Cl 4-Br H H CH(CH₃)₂ 3-Br, 5-Cl 4-Br H H CH(CH₃)₂ 3-Br, 5-Br4-Br H H CH(CH₃)₂ 3-CH₃, 5-CN 4-Br H H CH(CH₃)₂ 3-CH₃, 5-Cl 4-CF₃ H HCH(CH₃)₂ 3-Br, 5-Cl 4-CF₃ H H CH(CH₃)₂ 3-Br, 5-Br 4-CF₃ H H CH(CH₃)₂3-CH₃, 5-CN 4-CF₃ H H C(CH₃)₃ 3-CH₃, 5-Cl H H H C(CH₃)₃ 3-Br, 5-Cl H H HC(CH₃)₃ 3-Br, 5-Br H H H C(CH₃)₃ 3-CH₃, 5-CN H H H C(CH₃)₃ 3-CH₃, 5-Cl4-Cl H H C(CH₃)₃ 3-Br, 5-Cl 4-Cl H H C(CH₃)₃ 3-Br, 5-Br 4-Cl H H C(CH₃)₃3-CH₃, 5-CN 4-Cl H H C(CH₃)₃ 3-CH₃, 5-Cl 4-Br H H C(CH₃)₃ 3-Br, 5-Cl4-Br H H C(CH₃)₃ 3-Br, 5-Br 4-Br H H C(CH₃)₃ 3-CH₃, 5-CN 4-Br H HC(CH₃)₃ 3-CH₃, 5-Cl 4-CF₃ H H C(CH₃)₃ 3-Br, 5-Cl 4-CF₃ H H C(CH₃)₃ 3-Br,5-Br 4-CF₃ H H C(CH₃)₃ 3-CH₃, 5-CN 4-CF₃

TABLE 78 R¹ R² R³ (R⁴)_(n) (R^(14a))_(p) H H C(═O)OCH₃ 3-CH₃, 5-Cl H H HC(═O)OCH₃ 3-Br, 5-Cl H H H C(═O)OCH₃ 3-Br, 5-Br H H H C(═O)OCH₃ 3-CH₃,5-CN H H H C(═O)OCH₃ 3-CH₃, 5-Cl 4-Cl H H C(═O)OCH₃ 3-Br, 5-Cl 4-Cl H HC(═O)OCH₃ 3-Br, 5-Br 4-Cl H H C(═O)OCH₃ 3-CH₃, 5-CN 4-Cl H H C(═O)OCH₃3-CH₃, 5-Cl 4-Br H H C(═O)OCH₃ 3-Br, 5-Cl 4-Br H H C(═O)OCH₃ 3-Br, 5-Br4-Br H H C(═O)OCH₃ 3-CH₃, 5-CN 4-Br H H C(═O)OCH₃ 3-CH₃, 5-Cl 4-CF₃ H HC(═O)OCH₃ 3-Br, 5-Cl 4-CF₃ H H C(═O)OCH₃ 3-Br, 5-Br 4-CF₃ H H C(═O)OCH₃3-CH₃, 5-CN 4-CF₃ H H C(═O)N(CH₃)₂ 3-CH₃, 5-Cl H H H C(═O)N(CH₃)₂ 3-Br,5-Cl H H H C(═O)N(CH₃)₂ 3-Br, 5-Br H H H C(═O)N(CH₃)₂ 3-CH₃, 5-CN H H HC(═O)N(CH₃)₂ 3-CH₃, 5-Cl 4-Cl H H C(═O)N(CH₃)₂ 3-Br, 5-Cl 4-Cl H HC(═O)N(CH₃)₂ 3-Br, 5-Br 4-Cl H H C(═O)N(CH₃)₂ 3-CH₃, 5-CN 4-Cl H HC(═O)N(CH₃)₂ 3-CH₃, 5-Cl 4-Br H H C(═O)N(CH₃)₂ 3-Br, 5-Cl 4-Br H HC(═O)N(CH₃)₂ 3-Br, 5-Br 4-Br H H C(═O)N(CH₃)₂ 3-CH₃, 5-CN 4-Br H HC(═O)N(CH₃)₂ 3-CH₃, 5-Cl 4-CF₃ H H C(═O)N(CH₃)₂ 3-Br, 5-Cl 4-CF₃ H HC(═O)N(CH₃)₂ 3-Br, 5-Br 4-CF₃ H H C(═O)N(CH₃)₂ 3-CH₃, 5-CN 4-CF₃

TABLE 79 R¹ R² R³ (R⁴)_(n) (R^(14a))_(p) CH₃ CH₃ H 3-CH₃, 5-Cl H CH₃ CH₃H 3-Br, 5-Cl H CH₃ CH₃ H 3-Br, 5-Br H CH₃ CH₃ H 3-CH₃, 5-CN H CH₃ CH₃ H3-CH₃, 5-Cl 4-Cl CH₃ CH₃ H 3-Br, 5-Cl 4-Cl CH₃ CH₃ H 3-Br, 5-Br 4-Cl CH₃CH₃ H 3-CH₃, 5-CN 4-Cl CH₃ CH₃ H 3-CH₃, 5-Cl 4-Br CH₃ CH₃ H 3-Br, 5-Cl4-Br CH₃ CH₃ H 3-Br, 5-Br 4-Br CH₃ CH₃ H 3-CH₃, 5-CN 4-Br CH₃ CH₃ H3-CH₃, 5-Cl 4-CF₃ CH₃ CH₃ H 3-Br, 5-Cl 4-CF₃ CH₃ CH₃ H 3-Br, 5-Br 4-CF₃CH₃ CH₃ H 3-CH₃, 5-CN 4-CF₃ CH₃ H CH₃ 3-CH₃, 5-Cl H CH₃ H CH₃ 3-Br, 5-ClH CH₃ H CH₃ 3-Br, 5-Br H CH₃ H CH₃ 3-CH₃, 5-CN H CH₃ H CH₃ 3-CH₃, 5-Cl4-Cl CH₃ H CH₃ 3-Br, 5-Cl 4-Cl CH₃ H CH₃ 3-Br, 5-Br 4-Cl CH₃ H CH₃3-CH₃, 5-CN 4-Cl CH₃ H CH₃ 3-CH₃, 5-Cl 4-Br CH₃ H CH₃ 3-Br, 5-Cl 4-BrCH₃ H CH₃ 3-Br, 5-Br 4-Br CH₃ H CH₃ 3-CH₃, 5-CN 4-Br CH₃ H CH₃ 3-CH₃,5-Cl 4-CF₃ CH₃ H CH₃ 3-Br, 5-Cl 4-CF₃ CH₃ H CH₃ 3-Br, 5-Br 4-CF₃ CH₃ HCH₃ 3-CH₃, 5-CN 4-CF₃

TABLE 80 R¹ R² R³ (R⁴)_(n) (R^(14a))_(p) CH₃ CH₃ CH₃ 3-CH₃, 5-Cl H CH₃CH₃ CH₃ 3-Br, 5-Cl H CH₃ CH₃ CH₃ 3-Br, 5-Br H CH₃ CH₃ CH₃ 3-CH₃, 5-CN HCH₃ CH₃ CH₃ 3-CH₃, 5-Cl 4-Cl CH₃ CH₃ CH₃ 3-Br, 5-Cl 4-Cl CH₃ CH₃ CH₃3-Br, 5-Br 4-Cl CH₃ CH₃ CH₃ 3-CH₃, 5-CN 4-Cl CH₃ CH₃ CH₃ 3-CH₃, 5-Cl4-Br CH₃ CH₃ CH₃ 3-Br, 5-Cl 4-Br CH₃ CH₃ CH₃ 3-Br, 5-Br 4-Br CH₃ CH₃ CH₃3-CH₃, 5-CN 4-Br CH₃ CH₃ CH₃ 3-CH₃, 5-Cl 4-CF₃ CH₃ CH₃ CH₃ 3-Br, 5-Cl4-CF₃ CH₃ CH₃ CH₃ 3-Br, 5-Br 4-CF₃ CH₃ CH₃ CH₃ 3-CH₃, 5-CN 4-CF₃ CH₃ HCH₂CH₃ 3-CH₃, 5-Cl H CH₃ H CH₂CH₃ 3-Br, 5-Cl H CH₃ H CH₂CH₃ 3-Br, 5-Br HCH₃ H CH₂CH₃ 3-CH₃, 5-CN H CH₃ H CH₂CH₃ 3-CH₃, 5-Cl 4-Cl CH₃ H CH₂CH₃3-Br, 5-Cl 4-Cl CH₃ H CH₂CH₃ 3-Br, 5-Br 4-Cl CH₃ H CH₂CH₃ 3-CH₃, 5-CN4-Cl CH₃ H CH₂CH₃ 3-CH₃, 5-Cl 4-Br CH₃ H CH₂CH₃ 3-Br, 5-Cl 4-Br CH₃ HCH₂CH₃ 3-Br, 5-Br 4-Br CH₃ H CH₂CH₃ 3-CH₃, 5-CN 4-Br CH₃ H CH₂CH₃ 3-CH₃,5-Cl 4-CF₃ CH₃ H CH₂CH₃ 3-Br, 5-Cl 4-CF₃ CH₃ H CH₂CH₃ 3-Br, 5-Br 4-CF₃CH₃ H CH₂CH₃ 3-CH₃, 5-CN 4-CF₃

TABLE 81 R¹ R² R³ (R⁴)_(n) (R^(14a))_(p) CH₃ H CH(CH₃)₂ 3-CH₃, 5-Cl HCH₃ H CH(CH₃)₂ 3-Br, 5-Cl H CH₃ H CH(CH₃)₂ 3-Br, 5-Br H CH₃ H CH(CH₃)₂3-CH₃, 5-CN H CH₃ H CH(CH₃)₂ 3-CH₃, 5-Cl 4-Cl CH₃ H CH(CH₃)₂ 3-Br, 5-Cl4-Cl CH₃ H CH(CH₃)₂ 3-Br, 5-Br 4-Cl CH₃ H CH(CH₃)₂ 3-CH₃, 5-CN 4-Cl CH₃H CH(CH₃)₂ 3-CH₃, 5-Cl 4-Br CH₃ H CH(CH₃)₂ 3-Br, 5-Cl 4-Br CH₃ HCH(CH₃)₂ 3-Br, 5-Br 4-Br CH₃ H CH(CH₃)₂ 3-CH₃, 5-CN 4-Br CH₃ H CH(CH₃)₂3-CH₃, 5-Cl 4-CF₃ CH₃ H CH(CH₃)₂ 3-Br, 5-Cl 4-CF₃ CH₃ H CH(CH₃)₂ 3-Br,5-Br 4-CF₃ CH₃ H CH(CH₃)₂ 3-CH₃, 5-CN 4-CF₃ CH₃ H C(CH₃)₃ 3-CH₃, 5-Cl HCH₃ H C(CH₃)₃ 3-Br, 5-Cl H CH₃ H C(CH₃)₃ 3-Br, 5-Br H CH₃ H C(CH₃)₃3-CH₃, 5-CN H CH₃ H C(CH₃)₃ 3-CH₃, 5-Cl 4-Cl CH₃ H C(CH₃)₃ 3-Br, 5-Cl4-Cl CH₃ H C(CH₃)₃ 3-Br, 5-Br 4-Cl CH₃ H C(CH₃)₃ 3-CH₃, 5-CN 4-Cl CH₃ HC(CH₃)₃ 3-CH₃, 5-Cl 4-Br CH₃ H C(CH₃)₃ 3-Br, 5-Cl 4-Br CH₃ H C(CH₃)₃3-Br, 5-Br 4-Br CH₃ H C(CH₃)₃ 3-CH₃, 5-CN 4-Br CH₃ H C(CH₃)₃ 3-CH₃, 5-Cl4-CF₃ CH₃ H C(CH₃)₃ 3-Br, 5-Cl 4-CF₃ CH₃ H C(CH₃)₃ 3-Br, 5-Br 4-CF₃ CH₃H C(CH₃)₃ 3-CH₃, 5-CN 4-CF₃

TABLE 82 R¹ R² R³ (R⁴)_(n) (R^(14a))_(p) CH₃ H C(═O)OCH₃ 3-CH₃, 5-Cl HCH₃ H C(═O)OCH₃ 3-Br, 5-Cl H CH₃ H C(═O)OCH₃ 3-Br, 5-Br H CH₃ HC(═O)OCH₃ 3-CH₃, 5-CN H CH₃ H C(═O)OCH₃ 3-CH₃, 5-Cl 4-Cl CH₃ H C(═O)OCH₃3-Br, 5-Cl 4-Cl CH₃ H C(═O)OCH₃ 3-Br, 5-Br 4-Cl CH₃ H C(═O)OCH₃ 3-CH₃,5-CN 4-Cl CH₃ H C(═O)OCH₃ 3-CH₃, 5-Cl 4-Br CH₃ H C(═O)OCH₃ 3-Br, 5-Cl4-Br CH₃ H C(═O)OCH₃ 3-Br, 5-Br 4-Br CH₃ H C(═O)OCH₃ 3-CH₃, 5-CN 4-BrCH₃ H C(═O)OCH₃ 3-CH₃, 5-Cl 4-CF₃ CH₃ H C(═O)OCH₃ 3-Br, 5-Cl 4-CF₃ CH₃ HC(═O)OCH₃ 3-Br, 5-Br 4-CF₃ CH₃ H C(═O)OCH₃ 3-CH₃, 5-CN 4-CF₃ CH₃ HC(═O)N(CH₃)₂ 3-CH₃, 5-Cl H CH₃ H C(═O)N(CH₃)₂ 3-Br, 5-Cl H CH₃ HC(═O)N(CH₃)₂ 3-Br, 5-Br H CH₃ H C(═O)N(CH₃)₂ 3-CH₃, 5-CN H CH₃ HC(═O)N(CH₃)₂ 3-CH₃, 5-Cl 4-Cl CH₃ H C(═O)N(CH₃)₂ 3-Br, 5-Cl 4-Cl CH₃ HC(═O)N(CH₃)₂ 3-Br, 5-Br 4-Cl CH₃ H C(═O)N(CH₃)₂ 3-CH₃, 5-CN 4-Cl CH₃ HC(═O)N(CH₃)₂ 3-CH₃, 5-Cl 4-Br CH₃ H C(═O)N(CH₃)₂ 3-Br, 5-Cl 4-Br CH₃ HC(═O)N(CH₃)₂ 3-Br, 5-Br 4-Br CH₃ H C(═O)N(CH₃)₂ 3-CH₃, 5-CN 4-Br CH₃ HC(═O)N(CH₃)₂ 3-CH₃, 5-Cl 4-CF₃ CH₃ H C(═O)N(CH₃)₂ 3-Br, 5-Cl 4-CF₃ CH₃ HC(═O)N(CH₃)₂ 3-Br, 5-Br 4-CF₃ CH₃ H C(═O)N(CH₃)₂ 3-CH₃, 5-CN 4-CF₃ H CH₃H 3-Cl, 5-Cl H H CH₃ H 3-Cl, 5-Cl 4-Cl H CH₃ H 3-Cl, 5-Cl 4-Br H CH₃ H3-Cl, 5-Cl 4-CF₃ H CH₃ H 3-Cl, 5-Cl 4,5-Cl₂ H CH₃ H 3-Cl, 5-Cl 4,5-Br₂ HCH₃ H 3-CH₃, 5-Cl 4-Cl, 5-Br H CH₃ H 3-Br, 5-Cl 4-Cl, 5-Br H CH₃ H 3-Br,5-Br 4-Cl, 5-Br H CH₃ H 3-CH₃, 5-CN 4-Cl, 5-Br H CH₃ H 3-Cl, 5-Cl 4-Cl,5-Br H CH₃ H 3-CH₃, 5-Cl 4-Br, 5-Cl H CH₃ H 3-Br, 5-Cl 4-Br, 5-Cl H CH₃H 3-Br, 5-Br 4-Br, 5-Cl H CH₃ H 3-CH₃, 5-CN 4-Br, 5-Cl H CH₃ H 3-Cl,5-Cl 4-Br, 5-Cl H H CH₃ 3-Cl, 5-Cl H H H CH₃ 3-Cl, 5-Cl 4-Cl H H CH₃3-Cl, 5-Cl 4-Br H H CH₃ 3-Cl, 5-Cl 4-CF₃ H H CH₃ 3-Cl, 5-Cl 4,5-Cl₂ H HCH₃ 3-Cl, 5-Cl 4,5-Br₂ H H CH₃ 3-CH₃, 5-Cl 4-Cl, 5-Br H H CH₃ 3-Br, 5-Cl4-Cl, 5-Br H H CH₃ 3-Br, 5-Br 4-Cl, 5-Br H H CH₃ 3-CH₃, 5-CN 4-Cl, 5-BrH H CH₃ 3-Cl, 5-Cl 4-Cl, 5-Br H H CH₃ 3-CH₃, 5-Cl 4-Br, 5-Cl H H CH₃3-Br, 5-Cl 4-Br, 5-Cl H H CH₃ 3-Br, 5-Br 4-Br, 5-Cl H H CH₃ 3-CH₃, 5-CN4-Br, 5-Cl H H CH₃ 3-Cl, 5-Cl 4-Br, 5-Cl H CH₃ CH₃ 3-Cl, 5-Cl H H CH₃CH₃ 3-Cl, 5-Cl 4-Cl H CH₃ CH₃ 3-Cl, 5-Cl 4-Br H CH₃ CH₃ 3-Cl, 5-Cl 4-CF₃H CH₃ CH₃ 3-Cl, 5-Cl 4,5-Cl₂ H CH₃ CH₃ 3-Cl, 5-Cl 4,5-Br₂ H CH₃ CH₃3-CH₃, 5-Cl 4-Cl, 5-Br H CH₃ CH₃ 3-Br, 5-Cl 4-Cl, 5-Br H CH₃ CH₃ 3-Br,5-Br 4-Cl, 5-Br H CH₃ CH₃ 3-CH₃, 5-CN 4-Cl, 5-Br H CH₃ CH₃ 3-Cl, 5-Cl4-Cl, 5-Br H CH₃ CH₃ 3-CH₃, 5-Cl 4-Br, 5-Cl H CH₃ CH₃ 3-Br, 5-Cl 4-Br,5-Cl H CH₃ CH₃ 3-Br, 5-Br 4-Br, 5-Cl H CH₃ CH₃ 3-CH₃, 5-CN 4-Br, 5-Cl HCH₃ CH₃ 3-Cl, 5-Cl 4-Br, 5-Cl H H CH₂CH₃ 3-Cl, 5-Cl H H H CH₂CH₃ 3-Cl,5-Cl 4-Cl H H CH₂CH₃ 3-Cl, 5-Cl 4-Br H H CH₂CH₃ 3-Cl, 5-Cl 4-CF₃ H HCH(CH₃)₂ 3-Cl, 5-Cl H H H CH(CH₃)₂ 3-Cl, 5-Cl 4-Cl H H CH(CH₃)₂ 3-Cl,5-Cl 4-Br H H CH(CH₃)₂ 3-Cl, 5-Cl 4-CF₃ H H C(CH₃)₃ 3-Cl, 5-Cl H H HC(CH₃)₃ 3-Cl, 5-Cl 4-Cl H H C(CH₃)₃ 3-Cl, 5-Cl 4-Br H H C(CH₃)₃ 3-Cl,5-Cl 4-CF₃ H H C(═O)OCH₃ 3-Cl, 5-Cl H H H C(═O)OCH₃ 3-Cl, 5-Cl 4-Cl H HC(═O)OCH₃ 3-Cl, 5-Cl 4-Br H H C(═O)OCH₃ 3-Cl, 5-Cl 4-CF₃ H HC(═O)N(CH₃)₂ 3-Cl, 5-Cl H H H C(═O)N(CH₃)₂ 3-Cl, 5-Cl 4-Cl H HC(═O)N(CH₃)₂ 3-Cl, 5-Cl 4-Br H H C(═O)N(CH₃)₂ 3-Cl, 5-Cl 4-CF₃ CH₃ CH₃ H3-Cl, 5-Cl H CH₃ CH₃ H 3-Cl, 5-Cl 4-Cl CH₃ CH₃ H 3-Cl, 5-Cl 4-Br CH₃ CH₃H 3-Cl, 5-Cl 4-CF₃ CH₃ H CH₃ 3-Cl, 5-Cl H CH₃ H CH₃ 3-Cl, 5-Cl 4-Cl CH₃H CH₃ 3-Cl, 5-Cl 4-Br CH₃ H CH₃ 3-Cl, 5-Cl 4-CF₃ CH₃ CH₃ CH₃ 3-Cl, 5-ClH CH₃ CH₃ CH₃ 3-Cl, 5-Cl 4-Cl CH₃ CH₃ CH₃ 3-Cl, 5-Cl 4-Br CH₃ CH₃ CH₃3-Cl, 5-Cl 4-CF₃ CH₃ H CH₂CH₃ 3-Cl, 5-Cl H CH₃ H CH₂CH₃ 3-Cl, 5-Cl 4-ClCH₃ H CH₂CH₃ 3-Cl, 5-Cl 4-Br CH₃ H CH₂CH₃ 3-Cl, 5-Cl 4-CF₃ CH₃ HCH(CH₃)₂ 3-Cl, 5-Cl H CH₃ H CH(CH₃)₂ 3-Cl, 5-Cl 4-Cl CH₃ H CH(CH₃)₂3-Cl, 5-Cl 4-Br CH₃ H CH(CH₃)₂ 3-Cl, 5-Cl 4-CF₃ CH₃ H C(CH₃)₃ 3-Cl, 5-ClH CH₃ H C(CH₃)₃ 3-Cl, 5-Cl 4-Cl CH₃ H C(CH₃)₃ 3-Cl, 5-Cl 4-Br CH₃ HC(CH₃)₃ 3-Cl, 5-Cl 4-CF₃ CH₃ H C(═O)OCH₃ 3-Cl, 5-Cl H CH₃ H C(═O)OCH₃3-Cl, 5-Cl 4-Cl CH₃ H C(═O)OCH₃ 3-Cl, 5-Cl 4-Br CH₃ H C(═O)OCH₃ 3-Cl,5-Cl 4-CF₃ CH₃ H C(═O)N(CH₃)₂ 3-Cl, 5-Cl H CH₃ H C(═O)N(CH₃)₂ 3-Cl, 5-Cl4-Cl CH₃ H C(═O)N(CH₃)₂ 3-Cl, 5-Cl 4-Br CH₃ H C(═O)N(CH₃)₂ 3-Cl, 5-Cl4-CF₃

A compound represented by the formula (1-I):

wherein NR⁸R⁹, A³⁴, (R⁴)_(n), R¹³⁻² and (R^(14a))_(p) representcombinations shown in Table 83.

TABLE 83 NR⁸R⁹ A³⁴ (R⁴)_(n) R^(13a-2) (R^(14a))_(p) N(CH₃)₂ O 3-CH₃,5-Cl 3-chloro-2-pyridinyl H N(CH₃)₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl HN(CH₃)₂ O 3-Br, 5-Br 3-chloro-2-pyridinyl H N(CH₃)₂ O 3-CH₃, 5-CN3-chloro-2-pyridinyl H N(CH₃)₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl 4-ClN(CH₃)₂ O 3-Br, 5-Cl 3-chloro-2-pyridinyl 4-Cl N(CH₃)₂ O 3-Br, 5-Br3-chloro-2-pyridinyl 4-Cl N(CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl4-Cl N(CH₃)₂ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl 4-Br N(CH₃)₂ O 3-Br,5-Cl 3-chloro-2-pyridinyl 4-Br N(CH₃)₂ O 3-Br, 5-Br 3-chloro-2-pyridinyl4-Br N(CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl 4-Br N(CH₃)₂ O 3-CH₃,5-Cl 3-chloro-2-pyridinyl 4-CF₃ N(CH₃)₂ O 3-Br, 5-Cl3-chloro-2-pyridinyl 4-CF₃ N(CH₃)₂ O 3-Br, 5-Br 3-chloro-2-pyridinyl4-CF₃ N(CH₃)₂ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl 4-CF₃

A compound represented by the formula (1-K):

wherein R⁶, A³², (R⁴)_(n), R^(13a-3) and R^(14a-3) representcombinations shown in Table 84.

TABLE 84 R⁶ A³² (R⁴)_(n) R^(13a-3) R^(14a-3) CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl H CH₃ O3-Br, 5-Br 3-chloro-2-pyridinyl H CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinylH CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl Cl CH₃ O3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Br CH₃ O3-Br, 5-Br 3-chloro-2-pyridinyl Br CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl Br CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₃ O3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃CH₂CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl H CH₂CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl H CH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl H CH₂CH₃O 3-CH₃, 5-CN 3-chloro-2-pyridinyl H CH₂CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl CH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl ClCH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl Cl CH₂CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl CH₂CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl BrCH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Br CH₂CH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl Br CH₂CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl BrCH₂CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₂CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ CH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃CH₂CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

A compound represented by the formula (1-N):

wherein R⁶, A³², (R⁴)_(n), R^(13a-4) and R^(14a-4) representcombinations shown in Table 85.

TABLE 85 R⁶ A³² (R⁴)_(n) R^(13a-4) R^(14a-4) CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl H CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl H CH₃ O3-Br, 5-Br 3-chloro-2-pyridinyl H CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinylH CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl Cl CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl Cl CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl Cl CH₃ O3-CH₃, 5-CN 3-chloro-2-pyridinyl Cl CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Br CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Br CH₃ O3-Br, 5-Br 3-chloro-2-pyridinyl Br CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl Br CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₃ O3-Br, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl CF₃ CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃CH₂CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl H CH₂CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl H CH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl H CH₂CH₃O 3-CH₃, 5-CN 3-chloro-2-pyridinyl H CH₂CH₃ O 3-CH₃, 5-Cl3-chloro-2-pyridinyl Cl CH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl ClCH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl Cl CH₂CH₃ O 3-CH₃, 5-CN3-chloro-2-pyridinyl Cl CH₂CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl BrCH₂CH₃ O 3-Br, 5-Cl 3-chloro-2-pyridinyl Br CH₂CH₃ O 3-Br, 5-Br3-chloro-2-pyridinyl Br CH₂CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl BrCH₂CH₃ O 3-CH₃, 5-Cl 3-chloro-2-pyridinyl CF₃ CH₂CH₃ O 3-Br, 5-Cl3-chloro-2-pyridinyl CF₃ CH₂CH₃ O 3-Br, 5-Br 3-chloro-2-pyridinyl CF₃CH₂CH₃ O 3-CH₃, 5-CN 3-chloro-2-pyridinyl CF₃

A compound represented by the formula (1-Q):

wherein R⁶, A³², (R⁴)_(n), R^(13b-1), R^(14bz-1) and R^(14by-1)represent combinations shown in Table 86 to Table 89.

TABLE 86 R⁶ A³² (R⁴)_(n) R^(14bz-1) R^(14by-1) R^(13b-1) CH₃ O 3-CH₃,5-Cl 2-chlorophenyl H CH₃ CH₃ O 3-Br, 5-Cl 2-chlorophenyl H CH₃ CH₃ O3-Br, 5-Br 2-chlorophenyl H CH₃ CH₃ O 3-CH₃, 5-CN 2-chlorophenyl H CH₃CH₃ O 3-CH₃, 5-Cl 3-chloro- H CH₃ 2-pyridinyl CH₃ O 3-Br, 5-Cl 3-chloro-H CH₃ 2-pyridinyl CH₃ O 3-Br, 5-Br 3-chloro- H CH₃ 2-pyridinyl CH₃ O3-CH₃, 5-CN 3-chloro- H CH₃ 2-pyridinyl CH₃ O 3-CH₃, 5-Cl H2-chlorophenyl CH₃ CH₃ O 3-Br, 5-Cl H 2-chlorophenyl CH₃ CH₃ O 3-Br,5-Br H 2-chlorophenyl CH₃ CH₃ O 3-CH₃, 5-CN H 2-chlorophenyl CH₃ CH₃ O3-CH₃, 5-Cl H 3-chloro-2-pyridinyl CH₃ CH₃ O 3-Br, 5-Cl H3-chloro-2-pyridinyl CH₃ CH₃ O 3-Br, 5-Br H 3-chloro-2-pyridinyl CH₃ CH₃O 3-CH₃, 5-CN H 3-chloro-2-pyridinyl CH₃ CH₃ O 3-CH₃, 5-Cl2-chlorophenyl H C(CH₃)₃ CH₃ O 3-Br, 5-Cl 2-chlorophenyl H C(CH₃)₃ CH₃ O3-Br, 5-Br 2-chlorophenyl H C(CH₃)₃ CH₃ O 3-CH₃, 5-CN 2-chlorophenyl HC(CH₃)₃ CH₃ O 3-CH₃, 5-Cl 3-chloro- H C(CH₃)₃ 2-pyridinyl CH₃ O 3-Br,5-Cl 3-chloro- H C(CH₃)₃ 2-pyridinyl CH₃ O 3-Br, 5-Br 3-chloro- HC(CH₃)₃ 2-pyridinyl CH₃ O 3-CH₃, 5-CN 3-chloro- H C(CH₃)₃ 2-pyridinylCH₃ O 3-CH₃, 5-Cl H 2-chlorophenyl C(CH₃)₃ CH₃ O 3-Br, 5-Cl H2-chlorophenyl C(CH₃)₃ CH₃ O 3-Br, 5-Br H 2-chlorophenyl C(CH₃)₃ CH₃ O3-CH₃, 5-CN H 2-chlorophenyl C(CH₃)₃ CH₃ O 3-CH₃, 5-Cl H3-chloro-2-pyridinyl C(CH₃)₃ CH₃ O 3-Br, 5-Cl H 3-chloro-2-pyridinylC(CH₃)₃ CH₃ O 3-Br, 5-Br H 3-chloro-2-pyridinyl C(CH₃)₃ CH₃ O 3-CH₃,5-CN H 3-chloro-2-pyridinyl C(CH₃)₃

TABLE 87 R⁶ A³² (R⁴)_(n) R^(14bz-1) R^(14by-1) R^(13b-1) CH₃ O 3-CH₃,5-Cl 2-chlorophenyl H CH₂CF₃ CH₃ O 3-Br, 5-Cl 2-chlorophenyl H CH₂CF₃CH₃ O 3-Br, 5-Br 2-chlorophenyl H CH₂CF₃ CH₃ O 3-CH₃, 5-CN2-chlorophenyl H CH₂CF₃ CH₃ O 3-CH₃, 5-Cl 3-chloro- H CH₂CF₃ 2-pyridinylCH₃ O 3-Br, 5-Cl 3-chloro- H CH₂CF₃ 2-pyridinyl CH₃ O 3-Br, 5-Br3-chloro- H CH₂CF₃ 2-pyridinyl CH₃ O 3-CH₃, 5-CN 3-chloro- H CH₂CF₃2-pyridinyl CH₃ O 3-CH₃, 5-Cl H 2-chlorophenyl CH₂CF₃ CH₃ O 3-Br, 5-Cl H2-chlorophenyl CH₂CF₃ CH₃ O 3-Br, 5-Br H 2-chlorophenyl CH₂CF₃ CH₃ O3-CH₃, 5-CN H 2-chlorophenyl CH₂CF₃ CH₃ O 3-CH₃, 5-Cl H 3-chloro- CH₂CF₃2-pyridinyl CH₃ O 3-Br, 5-Cl H 3-chloro- CH₂CF₃ 2-pyridinyl CH₃ O 3-Br,5-Br H 3-chloro- CH₂CF₃ 2-pyridinyl CH₃ O 3-CH₃, 5-CN H 3-chloro- CH₂CF₃2-pyridinyl CH₂CH₃ O 3-CH₃, 5-Cl 2-chlorophenyl H CH₃ CH₂CH₃ O 3-Br,5-Cl 2-chlorophenyl H CH₃ CH₂CH₃ O 3-Br, 5-Br 2-chlorophenyl H CH₃CH₂CH₃ O 3-CH₃, 5-CN 2-chlorophenyl H CH₃ CH₂CH₃ O 3-CH₃, 5-Cl 3-chloro-H CH₃ 2-pyridinyl CH₂CH₃ O 3-Br, 5-Cl 3-chloro- H CH₃ 2-pyridinyl CH₂CH₃O 3-Br, 5-Br 3-chloro- H CH₃ 2-pyridinyl CH₂CH₃ O 3-CH₃, 5-CN 3-chloro-H CH₃ 2-pyridinyl CH₂CH₃ O 3-CH₃, 5-Cl H 2-chlorophenyl CH₃ CH₂CH₃ O3-Br, 5-Cl H 2-chlorophenyl CH₃ CH₂CH₃ O 3-Br, 5-Br H 2-chlorophenyl CH₃CH₂CH₃ O 3-CH₃, 5-CN H 2-chlorophenyl CH₃ CH₂CH₃ O 3-CH₃, 5-Cl H3-chloro- CH₃ 2-pyridinyl CH₂CH₃ O 3-Br, 5-Cl H 3-chloro- CH₃2-pyridinyl CH₂CH₃ O 3-Br, 5-Br H 3-chloro- CH₃ 2-pyridinyl CH₂CH₃ O3-CH₃, 5-CN H 3-chloro- CH₃ 2-pyridinyl

TABLE 88 R⁶ A³² (R⁴)_(n) R^(14bz-1) R^(14by-1) R^(13b-1) CH₂CH₃ O 3-CH₃,5-Cl 2-chlorophenyl H C(CH₃)₃ CH₂CH₃ O 3-Br, 5-Cl 2-chlorophenyl HC(CH₃)₃ CH₂CH₃ O 3-Br, 5-Br 2-chlorophenyl H C(CH₃)₃ CH₂CH₃ O 3-CH₃,5-CN 2-chlorophenyl H C(CH₃)₃ CH₂CH₃ O 3-CH₃, 5-Cl 3-chloro- H C(CH₃)₃2-pyridinyl CH₂CH₃ O 3-Br, 5-Cl 3-chloro- H C(CH₃)₃ 2-pyridinyl CH₂CH₃ O3-Br, 5-Br 3-chloro- H C(CH₃)₃ 2-pyridinyl CH₂CH₃ O 3-CH₃, 5-CN3-chloro- H C(CH₃)₃ 2-pyridinyl CH₂CH₃ O 3-CH₃, 5-Cl H 2-chlorophenylC(CH₃)₃ CH₂CH₃ O 3-Br, 5-Cl H 2-chlorophenyl C(CH₃)₃ CH₂CH₃ O 3-Br, 5-BrH 2-chlorophenyl C(CH₃)₃ CH₂CH₃ O 3-CH₃, 5-CN H 2-chlorophenyl C(CH₃)₃CH₂CH₃ O 3-CH₃, 5-Cl H 3-chloro- C(CH₃)₃ 2-pyridinyl CH₂CH₃ O 3-Br, 5-ClH 3-chloro- C(CH₃)₃ 2-pyridinyl CH₂CH₃ O 3-Br, 5-Br H 3-chloro- C(CH₃)₃2-pyridinyl CH₂CH₃ O 3-CH₃, 5-CN H 3-chloro- C(CH₃)₃ 2-pyridinyl CH₂CH₃O 3-CH₃, 5-Cl 2-chlorophenyl H CH₂CF₃ CH₂CH₃ O 3-Br, 5-Cl 2-chlorophenylH CH₂CF₃ CH₂CH₃ O 3-Br, 5-Br 2-chlorophenyl H CH₂CF₃ CH₂CH₃ O 3-CH₃,5-CN 2-chlorophenyl H CH₂CF₃ CH₂CH₃ O 3-CH₃, 5-Cl 3-chloro- H CH₂CF₃2-pyridinyl CH₂CH₃ O 3-Br, 5-Cl 3-chloro- H CH₂CF₃ 2-pyridinyl CH₂CH₃ O3-Br, 5-Br 3-chloro- H CH₂CF₃ 2-pyridinyl CH₂CH₃ O 3-CH₃, 5-CN 3-chloro-H CH₂CF₃ 2-pyridinyl CH₂CH₃ O 3-CH₃, 5-Cl H 2-chlorophenyl CH₂CF₃ CH₂CH₃O 3-Br, 5-Cl H 2-chlorophenyl CH₂CF₃ CH₂CH₃ O 3-Br, 5-Br H2-chlorophenyl CH₂CF₃ CH₂CH₃ O 3-CH₃, 5-CN H 2-chlorophenyl CH₂CF₃CH₂CH₃ O 3-CH₃, 5-Cl H 3-chloro- CH₂CF₃ 2-pyridinyl CH₂CH₃ O 3-Br, 5-ClH 3-chloro- CH₂CF₃ 2-pyridinyl CH₂CH₃ O 3-Br, 5-Br H 3-chloro- CH₂CF₃2-pyridinyl CH₂CH₃ O 3-CH₃, 5-CN H 3-chloro- CH₂CF₃ 2-pyridinyl

TABLE 89 R⁶ A³² (R⁴)_(n) R^(14bz-1) R^(14by-1) R^(13b-1) CH₃ O 3-CH₃,5-Cl 2-chlorophenyl H CHF₂ CH₃ O 3-Br, 5-Cl 2-chlorophenyl H CHF₂ CH₃ O3-Br, 5-Br 2-chlorophenyl H CHF₂ CH₃ O 3-CH₃, 5-CN 2-chlorophenyl H CHF₂CH₃ O 3-CH₃, 5-Cl 3-chloro- H CHF₂ 2-pyridinyl CH₃ O 3-Br, 5-Cl3-chloro- H CHF₂ 2-pyridinyl CH₃ O 3-Br, 5-Br 3-chloro- H CHF₂2-pyridinyl CH₃ O 3-CH₃, 5-CN 3-chloro- H CHF₂ 2-pyridinyl CH₃ O 3-CH₃,5-Cl H 2-chlorophenyl CHF₂ CH₃ O 3-Br, 5-Cl H 2-chlorophenyl CHF₂ CH₃ O3-Br, 5-Br H 2-chlorophenyl CHF₂ CH₃ O 3-CH₃, 5-CN H 2-chlorophenyl CHF₂CH₃ O 3-CH₃, 5-Cl H 3-chloro- CHF₂ 2-pyridinyl CH₃ O 3-Br, 5-Cl H3-chloro- CHF₂ 2-pyridinyl CH₃ O 3-Br, 5-Br H 3-chloro- CHF₂ 2-pyridinylCH₃ O 3-CH₃, 5-CN H 3-chloro- CHF₂ 2-pyridinyl CH₃ O 3-CH₃, 5-Cl2-chlorophenyl H CBrF₂ CH₃ O 3-Br, 5-Cl 2-chlorophenyl H CBrF₂ CH₃ O3-Br, 5-Br 2-chlorophenyl H CBrF₂ CH₃ O 3-CH₃, 5-CN 2-chlorophenyl HCBrF₂ CH₃ O 3-CH₃, 5-Cl 3-chloro- H CBrF₂ 2-pyridinyl CH₃ O 3-Br, 5-Cl3-chloro- H CBrF₂ 2-pyridinyl CH₃ O 3-Br, 5-Br 3-chloro- H CBrF₂2-pyridinyl CH₃ O 3-CH₃, 5-CN 3-chloro- H CBrF₂ 2-pyridinyl CH₃ O 3-CH₃,5-Cl H 2-chlorophenyl CBrF₂ CH₃ O 3-Br, 5-Cl H 2-chlorophenyl CBrF₂ CH₃O 3-Br, 5-Br H 2-chlorophenyl CBrF₂ CH₃ O 3-CH₃, 5-CN H 2-chlorophenylCBrF₂ CH₃ O 3-CH₃, 5-Cl H 3-chloro- CBrF₂ 2-pyridinyl CH₃ O 3-Br, 5-Cl H3-chloro- CBrF₂ 2-pyridinyl CH₃ O 3-Br, 5-Br H 3-chloro- CBrF₂2-pyridinyl CH₃ O 3-CH₃, 5-CN H 3-chloro- CBrF₂ 2-pyridinyl

Examples of the pests against which the present compound has controllingefficacy include harmful arthropods such as harmful insects and harmfulmites, and nemathelminths such as nematodes, and specific examples areas shown below.

Hemiptera:—

Planthoppers (Delphacidae) such as small brown planthopper (Laodelphaxstriatellus), brown rice planthopper (Nilaparvata lugens), andwhite-backed rice planthopper (Sogatella furcifera); leafhoppers(Deltocephalidae) such as green rice leafhopper (Nephotettixcincticeps), green rice leafhopper (Nephotettix virescens), and teagreen leafhopper (Empoasca onukii); aphids (Aphididae) such as cottonaphid (Aphis gossypii), green peach aphid (Myzus persicae), cabbageaphid (Brevicoryne brassicae), spiraea aphid (Aphis spiraecola), potatoaphid (Macrosiphum euphorbiae), foxglove aphid (Aulacorthum solani), oatbird-cherry aphid (Rhopalosiphum padi), tropical citrus aphid (Toxopteracitricidus), and mealy plum aphid (Hyalopterus pruni); stink bugs(Pentatomidae) such as green stink bug (Nezara antennata) bean bug(Riptortus clavetus), rice bug (Leptocorisa chinensis), white spottedspined bug (Eysarcoris parvus), and stink bug (Halyomorpha mista);whiteflies (Aleyrodidae) such as greenhouse whitefly (Trialeurodesvaporariorum), sweetpotato whitefly (Bemisia tabaci), silver leafwhitefly (Bemisia argentifolii), citrus whitefly (Dialeurodes citri),and citrus spiny white fly (Aleurocanthus spiniferus); scales (Coccidae)such as Calformia red scale (Aonidiella aurantii), San Jose scale(Comstockaspis perniciosa), citrus north scale (Unaspis citri), red waxscale (Ceroplastes rubens), cottonycushion scale (Icerya purchasi),Japanese mealybug (Planococcus kraunhiae), Cosmstock mealybug(Pseudococcus longispinis), and white peach scale (Pseudaulacaspispentagona); lace bags (Tingidae); psyllids (Psyllidae); etc.

Lepidoptera:—

Pyralid moths (Pyralidae) such as rice stem borer (Chilo suppressalis),yellow rice borer (Tryporyza incertulas), rice leafroller(Cnaphalocrocis medinalis), cotton leafroller (Notarcha derogata),Indian meal moth (Plodia interpunctella), oriental corn borer (Ostriniafurnacalis), cabbage webworm (Hellula undalis), and bluegrass webworm(Pediasia teterrellus); owlet moths (Noctuidae) such as common cutworm(Spodoptera litura), beet armyworm (Spodoptera exigua), armyworm(Pseudaletia separata), cabbage armyworm (Mamestra brassicae), blackcutworm (Agrotis ipsilon), beet semi-looper (Plusia nigrisigna),Thoricoplusia spp., Heliothis spp., and Helicoverpa spp.; whites andsulfer butterflies (Pieridae) such as common white (Pieris rapae);tortricid moths (Tortricidae) such as Adoxophyes spp., oriental fruitmoth (Grapholita molesta), soybean pod borer (Leguminivoraglycinivorella), azuki bean podworm (Matsumuraeses azukivora), summerfruit tortrix (Adoxophyes orana fasciata), Adoxophyes sp., oriental teatortrix (Homona magnanima), apple tortrix (Archips fuscocupreanus), andCydia pomonella; leafblotch miners (Gracillariidae) such as tealeafroller (Caloptilia theivora), and apple leafminer (Phyllonorycterringoneella); Carposinidae such as peach fruit moth (Carposinaniponensis); lyonetiid moths (Lyonetiidae) such as Lyonetia spp.;tussock moths (Lymantriidae) such as Lyymantria spp., and Euproctisspp.; yponomeutid moths (Yponomeutidae) such as diamondback (Plutellaxylostella); gelechiid moths (Gelechiidae) such as pink bollworm(Pectinophora gossypiella), and potato tubeworm (Phthorimaeaoperculella); tiger moths and allies (Arctiidae) such as fall webworm(Hyphantria cunea); tineid moths (Tineidae) such as casemaking clothesmoth (Tinea translucens), and webbing clothes moth (Tineolabisselliella); etc.

Thysanoptera:—

Thrips (Thripidae) such as yellow citrus thrips (Frankliniellaoccidentalis), Thrips parmi, yellow tea thrips (Scirtothrips dorsalis),onion thrip (Thrips tabaci), flower thrips (Frankliniella intonsa), etc.

Diptera: —

Housefly (Musca domestica), common mosquito (Culex popiens pallens),horsefly (Tabanus trigonus), onion maggot (Hylemya antiqua), seedcornmaggot (Hylemya platura), Anopheles sinensis, rice leafminer (Agromyzaoryzae), rice leafminer (Hydrellia griseola), rice stem maggot (Chloropsoryzae), melon fly (Dacus cucurbitae), Ceratitis capitata, legumeleafminer (Liriomyza trifolii), tomato leafminer (Liriomyza sativae),garden pea leafminer (Chromatomyia horticola), etc.

Coleoptera:—

Twenty-eight-spotted ladybird (Epilachna vigintioctopunctata), cucurbitleaf beetle (Aulacophora femoralis), striped flea beetle (Phyllotretastriolata), rice leaf beetle (Oulema oryzae), rice curculio(Echinocnemus squameus), rice water weevil (Lissorhoptrus oryzophilus),Anthonomus grandis, azuki bean weevil (Callosobruchus chinensis),Sphenophorus venatus, Japanese beetle (Popillia japonica), cupreouschafer (Anomala cuprea), corn root worm (Diabrotica spp.), Coloradobeetle (Leptinotarsa decemlineata), click beetle (Agriotes spp.),cigarette beetle (Lasioderma serricorne), varied carper beetle(Anthrenus verbasci), red flour beetle (Tribolium castaneum), powderpost beetle (Lyctus brunneus), white-spotted longicorn beetle(Anoplophora malasiaca), pine shoot beetle (Tomicus piniperda), etc.

Orthoptera:—

Asiatic locust (Locusta migratoria), African mole cricket (Gryllotalpaafricana), rice grasshopper (Oxya yezoensis), rice grasshopper (Oxyajaponica), etc.

Hymenoptera:—

Cabbage sawfly (Athalia rosae), Acromyrmex spp., fire ant (Solenopsisspp.), etc.

Nematodes:—

Rice white-tip nematode (Aphelenchoides besseyi), strawberry budnematode (Nothotylenchus acris), southern root-knot nematode(Meloidogyne incognita), northern root-knot nematode (Meloidogynehapla), Javanese root-knot nematode (Meloidogyne javanica), soybean cystnematode (Heterodera glycines), potato cyst nematode (Globoderarostochiensis), coffee root-lesion nematode (Pratylenchus coffeae),California root-lesion nematode (Pratylenchus neglectus), etc.

Dictyoptera:—

German cockroach (Blattella germanica), smokybrown cockroach(Periplaneta fuliginosa), American cockroach (Periplaneta americana),Periplaneta brunnea, oriental cockroach (Blatta orientalis), etc.

Acarina:—

Spider mites (Tetranychidae) such as two-spotted spider mite(Tetranychus urticae), Kanzawa spider mite (Tetranychus kanzawai),citrus red mite (Panonychus citri), European red mite (Panonychus ulmi),and Oligonychus spp.; eriophyid mites (Eriophyidae) such as pink citrusrust mite (Aculops pelekassi), pink citrus rust mite (Phyllocoptrutacitri), tomato rust mite (Aculops lycopersici), purple tea mite(Calacarus carinatus), pink tea rust mite (Acaphylla theavagran), andEriophyes chibaensis; tarosonemid mites (Tarsonemidae) such as broadmite (Polyphagotarsonemus latus); false spider mites (Tenuipalpidae)such as Brevipalpus phoenicis; Tuckerellidae; ticks (Ixodidae) such asHaemaphysalis longicornis, Haemaphysalis flava, Dermacentor taiwanicus,Ixodes ovatus, Ixodes persulcatus, Boophilus microplus, andRhipicephalus sanguineus; acarid mites (Acaridae) such as mold mite(Tyrophagus putrescentiae), and Tyrophagus similis; house dust mites(Pyroglyphidae) such as Dermatophagoides farinae, and Dermatophagoidesptrenyssnus; cheyletide mites (Cheyletidae) such as Cheyletus eruditus,Cheyletus malaccensis, and Cheyletus moorei; parasitoid mites(Dermanyssidae); etc.

The pesticide of the present invention may be the present compounditself but, usually, the present compound is mixed with an inert carriersuch as a solid carrier, a liquid carrier, a gaseous carrier and thelike and, if necessary, a surfactant, and other preparation additivesare added to formulate into a composition or a preparation such as anemulsion, oil, powder, granules, a wettable preparation, a flowablepreparation, microcapsules, an aerosol, a fumigant, poison bait, a resinpreparation or the like. These compositions or preparations usuallycontain 0.01 to 95% by weight of the present compound.

Examples of the solid carrier to be used include fine powders andgranules such as clays (kaolin clay, diatomaceous earth, bentonite,fubasami clay, acid clay, etc.), synthetic hydrous silicon oxide, talc,ceramic, other inorganic minerals (sericite, quartz, sulfur, activecarbon, calcium carbonate, hydrated silica, etc.), chemical fertilizers(ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammoniumchloride, etc.) and the like.

Examples of the liquid carrier include water, alcohols (methanol,ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, ethyleneglycol, propylene glycol, phenoxyethanol, etc.), ketones (acetone,methyl ethyl ketone, cyclohexanone, etc.), aromatic hydrocarbons(toluene, xylene, ethylbenzene, dodecylbenzene, phenylxylylethane,methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane,kerosene, gas oil, etc.), esters (ethyl acetate, butyl acetate,isopropyl myristate, ethyl oleate, diisopropyl adipate, diisobutyladipate, propylene glycol monomethyl ether acetate, etc.), nitriles(acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether,1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethylether, diethylene glycol monomethyl ether, propylene glycol monomethylether, dipropylene glycol monomethyl ether,3-methoxyl-3-methyl-1-butanol, etc.), acid amides(N,N-dimethylformamide, N,N-dimethylacetamide, etc.), halogenatedhydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride,etc.), sulfoxides (dimethyl sulfoxide, etc.), carbonic propylene andvegetable oils (soybean oil, cottonseed oil, etc.).

Examples of the gaseous carrier include fluorocarbon, butane gas, LPG(liquefied petroleum gas), dimethyl ether, and carbonic acid gas.

Examples of the surfactant include nonionic surfactants such aspolyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether,polyethylene glycol fatty acid ester, and the like, and anionicsurfactants such as alkyl sulfonate salts, alkylbenzene sulfonate saltsand alkyl sulfate salts.

Examples of other preparation additives include binders, dispersingagents, coloring agents and stabilizers, specifically, casein, gelatin,sugars (starch, gum arabic, cellulose derivatives, alginic acid, etc.),lignin derivatives, bentonite, synthetic water-soluble polymers(polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids, etc.), PAP(acidic isopropyl phosphate), BHT (2,6-di-tert-butyl-4-methylphenol),and BHA (a mixture of 2-tert-butyl-4-methoxyphenol and3-tert-butyl-4-methoxyphenol).

The method of controlling a pest of the present invention is usuallyperformed by applying the pesticide of the present invention directly toa pest or to a place where a pest inhabits (plant, soil, in house,animal, etc.).

When the pesticide of the present invention is used for controlling apest in the agricultural field, an amount to be applied is usually 1 to10,000 g per 10,000 m² in terms of the amount of the present compound.When the pesticide of the present invention is formulated into anemulsion, a wettable preparation, a flowable preparation or the like,usually, the agent is applied by diluting with water so that the activeingredient concentration becomes 0.01 to 10,000 ppm, and granules,powder or the like are usually applied as they are.

These preparations, or preparations diluted with water may be directlyapplied to a pest or to a plant such as a crop to be protected against apest, or may be applied to soil of a cultivated land in order to controla pest inhabiting in the soil.

Alternatively, treatment may be performed for example, by winding asheet-like or string-like-processed resin preparation on a crop,surrounding a crop with the resin preparation, or laying the resinpreparation on soil about roots of a crop.

When the pesticide of the present invention is used for controlling apest which inhabits in a house (e.g. fly, mosquito, cockroach, etc.),the amount to be applied is usually 0.01 to 1000 mg per 1 m² of treatingarea in terms of the amount of the present compound in case of surfacetreatment, and is usually 0.01 to 500 mg per 1 m³ of treating space interms of the amount of the present of compound in case of spatialtreatment. When the pesticide of the present invention is formulatedinto an emulsion, a wettable preparation, a flowable preparation or thelike, usually, the agent is applied by diluting with water so that theactive ingredient concentration becomes 0.1 to 1000 ppm, and oil, anaerosol, a fumigant, poison bait or the like is applied as it is.

The pesticide of the present invention may contain other harmfularthropod controlling agents, acaricides, nematicides, fungicides,herbicides, plant growth regulators, synergists, fertilizers, soilconditioners, animal feeds, and the like.

As the active ingredients of the aforementioned other harmful arthropodcontrolling agents, acaricides and/or nematicides, for example, thefollowing compounds can be mentioned.

(1) Organic Phosphorus Compounds

Acephate, aluminium phosphide, butathiofos, cadusafos, chlorethoxyfos,chlorfenvinphos, chlorpyrifos, chlorpyrifos-methyl, cyanophos: CYAP,diazinon, DCIP (dichlorodiisopropyl ether), dichlofenthion: ECP,dichlorvos: DDVP, dimethoate, dimethylvinphos, disulfoton, EPN, ethion,ethoprophos, etrimfos, fenthion: MPP, fenitrothion: MEP, fosthiazate,formothion, hydrogen phosphide, isofenphos, isoxathion, malathion,mesulfenfos, methidathion: DMTP, monocrotophos, naled: BRP,oxydeprofos:ESP, parathion, phosalone, phosmet: PMP, pirimiphos-methyl,pyridafenthion, quinalphos, phenthoate: PAP, profenofos, propaphos,prothiofos, pyraclorfos, salithion, sulprofos, tebupirimfos, temephos,tetrachlorvinphos, terbufos, thiometon, trichlorphon:DEP, vamidothion,and the like.

(2) Carbamate Compounds

Alanycarb, bendiocarb, benfuracarb, BPMC, carbaryl, carbofuran,carbosulfan, cloethocarb, ethiofencarb, fenobucarb, fenothiocarb,fenoxycarb, furathiocarb, isoprocarb: MIPC, metolcarb, methomyl,methiocarb, NAC, oxamyl, pirimicarb, propoxur: PHC, XMC, thiodicarb,xylylcarb, and the like.

(3) Synthetic Pyrethroid Compounds

Acrinathrin, allethrin, benfluthrin, beta-cyfluthrin, bifenthrin,cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, deltamethrin,esfenvalerate, ethofenprox, fenpropathrin, fenvalerate, flucythrinate,flufenoprox, flumethrin, fluvalinate, halfenprox, imiprothrin,permethrin, prallethrin, pyrethrins, resmethrin, sigma-cypermethrin,silafluofen, tefluthrin, tralomethrin, transfluthrin,2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl (EZ)-(1RS, 3RS;1RS,3SR)-2,2-dimethyl-3-prop-1-enylcyclopropanecarboxylate,2,3,5,6-tetrafluoro-4-methylbenzyl (EZ)-(1RS,3RS;1RS,3SR)-2,2-dimethyl-3-prop-1-enylcyclopropanecarboxylate,2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl(1RS,3RS;1RS,3SR)-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate,and the like.

(4) Nereistoxin Compounds

Cartap, bensultap, thiocyclam, monosultap, bisultap, and the like.

(5) Neonicotinoid Compounds

Imidacloprid, nitenpyram, acetamiprid, thiamethoxam, thiacloprid,dinotefuran, clothianidin, and the like.

(6) Benzoylurea Compounds

Chlorfluazuron, bistrifluoron, diafenthiuron, diflubenzuron, fluazuron,flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron,noviflumuron, teflubenzuron, triflumuron, and the like.

(7) Phenylpyrazole Compounds

Acetoprole, ethiprole, fipronil, vaniliprole, pyriprole, pyrafluprole,and the like.

(8) Bt Toxin Insecticides

Viable endospores derived from Bacillus thuringiensis and crystallinetoxins produced by it, as well as a mixture of thereof.

(9) Hydrazine Compounds

Chromafenozide, halofenozide, methoxyfenozide, tebufenozide, and thelike.

(10) Organic Chlorine Compounds

Aldrin, dieldrin, dienochlor, endosulfan, methoxychlor, and the like.

(11) Natural Insecticides

Machine oil, nicotine-sulfate, and the like.

(12) Other Insecticides

Avermectin-B, bromopropylate, buprofezin, chlorphenapyr, cyromazine,1,3-Dichloropropene, emamectin-benzoate, fenazaquin, flupyrazofos,hydroprene, indoxacarb, metoxadiazone, milbemycin-A, pymetrozine,pyridalyl, pyriproxyfen, spinosad, sulfluramid, tolfenpyrad, triazamate,flubendiamide, SI-0009, cyflumetofen, arsenic acid, benclothiaz, calciumcyanamide, calcium polysulfide, chlordane, DDT, DSP, flufenerim,flonicamid, flurimfen, formetanate, metam-ammonium, metam-sodium, Methylbromide, nidinotefuran, Potassium oleate, protrifenbute, spiromesifen,sulfur, metaflumizone, spirotetramat, and the like.

Acaricides

Acequinocyl, amitraz, benzoximate, bromopropylate, chinomethionat,chlorobenzilate, CPCBS(chlorfenson), clofentezine, Kelthane(dicofol),etoxazole, fenbutatinoxide, fenothiocarb, fenpyroximate, fluacrypyrim,fluproxyfen, hexythiazox, propargite:BPPS, polynactins, pyridaben,Pyrimidifen, tebufenpyrad, tetradifon, spirodiclofen, amidoflumet,Bifenazate, Cyflumetofen, and the like. Nematicides (nematicidal activeingredients)

DCIP, fosthiazate, levamisol, methylsothiocyanate, morantel tartarate,and the like.

The present invention will be explained in more detail below by way ofPreparation Examples, Formulation Examples, Test Examples, but thepresent invention is not limited to these Examples.

First, Preparation Examples of the present compound will be explained.

PREPARATION EXAMPLE 1

A mixture of 0.22 g of N-(2-aminobenzoyl)-N′-ethoxycarbonylhydrazine,0.31 g of1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carbonylchloride and 10 ml of pyridine was stirred at room temperature for 2hours. Water was poured into the reaction mixture, and a depositedprecipitate was collected by filtration to obtain 0.13 g of the presentcompound (1) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.35 (3H, t, J=8 Hz), 4.29 (2H, q, J=8 Hz),6.85 (1H, brs), 7.10 (1H, t, J=8 Hz), 7.24 (1H, s), 7.44 (1H, t, J=8Hz), 7.47 (1H, dd, J=8 Hz, 4 Hz), 7.62 (1H, d, J=8 Hz), 7.93 (1H, d, J=4Hz), 8.42 (1H, brs), 8.46 (1H, d, J=8 Hz), 8.52 (1H, d, J=8 Hz), 11.86(1H, brs)

PREPARATION EXAMPLE 2

A mixture of 0.13 g of 1-methyl-1H-pyrrole-2-carboxylic acid, 0.15 g ofthionyl chloride and 5 ml of hexane was heated under reflux for 2 hours.The reaction mixture was concentrated under reduced pressure to obtain0.14 g of 1-methyl-1H-pyrrole-2-carbonyl chloride. To a mixture of 0.22g of N-(2-aminobenzoyl)-N′-ethoxycarbonylhydrazine and 10 ml of pyridinewas added 0.14 g of the resulting 1-methyl-1H-pyrrole-2-carbonylchloride, and the mixture was stirred at room temperature for 2 hours.Water was poured into the reaction mixture, and a deposited precipitatewas collected by filtration to obtain 0.11 g of the present compound (2)of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.02-1.28 (3H, m), 3.91 (3H, s),4.00-4.16 (2H, m), 6.13 (1H, d, J=4 Hz), 6.78 (1H, d, J=4 Hz), 7.06 (1H,m), 7.15 (1H, t, J=8 Hz), 7.56 (1H, t, J=8 Hz), 7.79 (1H, d, J=8 Hz),8.57 (1H, d, J=8 Hz), 9.30 (1H, brs), 10.57 (1H, brs), 11.63 (1H, brs)

PREPARATION EXAMPLE 3

A mixture of 0.19 g of1-methyl-3-trifluoromethyl-1H-pyrazole-5-carboxylic acid, 0.15 g ofthionyl chloride and 5 ml of hexane was heated under reflux for 2 hours.The reaction mixture was concentrated under reduced pressure to obtain0.14 g of 1-methyl-3-trifluoromethyl-1H-pyrazole-5-carbonyl chloride. Toa mixture of 0.22 g of N-(2-aminobenzoyl)-N′-ethoxycarbonylhydrazine and10 ml of pyridine was added 0.14 g of the resulting1-methyl-3-trifluoromethyl-1H-pyrazole-5-carbonyl chloride and themixture was stirred at room temperature for 2 hours. Water was pouredinto the reaction mixture, and a deposited precipitates were collectedby filtration to obtain 0.23 g of the present compound (3) of theformula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.20 (3H, t, J=8 Hz), 4.10 (2H, q, J=8Hz), 4.19 (3H, s), 7.17 (1H, s), 7.28 (1H, t, J=8 Hz), 7.60 (1H, t, J=8Hz), 7.79 (1H, d, J=8 Hz), 8.37 (1H, d, J=8 Hz), 9.02 (1H, brs), 10.41(1H, brs), 11.50 (1H, brs)

PREPARATION EXAMPLE 4

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.06 g of ethyl chloroformate and 10 ml of pyridine was stirred at roomtemperature for 2 hours. Water was poured into the reaction mixture, anda deposited precipitate was collected by filtration to obtain 0.08 g ofthe present compound (4) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 0.96-1.26 (3H, m), 2.16 (3H, s),3.90-4.12 (2H, m), 7.38 (1H, s), 7.55 (1H, s), 7.66 (1H, dd, J=8 Hz, 4Hz), 7.71 (1H, s), 8.22 (1H, d, J=8 Hz), 8.53 (1H, d, J=4 Hz), 9.25 (1H,brs), 10.14 (1H, brs), 10.37 (1H, brs)

PREPARATION EXAMPLE 5

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.05 g of methyl chloroformate and 10 ml of pyridine was stirred at roomtemperature for 2 hours. Water was poured into the reaction mixture, anda deposited precipitate was collected by filtration to obtain 0.16 g ofthe present compound (5) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.16 (3H, s), 3.62 (3H, s), 7.39 (1H, s),7.56 (1H, s), 7.67 (1H, dd, J=8 Hz, 4 Hz), 7.70 (1H, s), 8.22 (1H, d,J=8 Hz), 8.54 (1H, d, J=4 Hz), 9.31 (1H, brs), 10.17 (1H, brs), 10.38(1H, brs)

PREPARATION EXAMPLE 6

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.05 g of isopropyl chloroformate and 10 ml of pyridine was stirred atroom temperature for 2 hours. Water was poured into the reactionmixture, and a deposited precipitate was collected by filtration toobtain 0.21 g of the present compound (6) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 0.97-1.31 (6H, m), 2.16 (3H, s),4.68-4.89 (1H, m), 7.38 (1H, s), 7.55 (1H, s), 7.66 (1H, dd, J=8 Hz, 4Hz), 7.71 (1H, s), 8.22 (1H, d, J=8 Hz), 8.53 (1H, d, J=4 Hz), 9.18 (1H,brs), 10.12 (1H, brs), 10.37 (1H, brs)

PREPARATION EXAMPLE 7

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.05 g of cyclopropanecarbonyl chloride and 10 ml of pyridine wasstirred at room temperature for 2 hours. Water was poured into thereaction mixture, and a deposited precipitate was collected byfiltration to obtain 0.20 g of the present compound (7) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 0.57-0.82 (4H, m), 1.63-1.73 (1H, m),2.16 (3H, s), 7.43 (1H, s), 7.54 (1H, s), 7.66 (1H, dd, J=8 Hz, 4 Hz),7.74 (1H, s), 8.22 (1H, d, J=8 Hz), 8.53 (1H, d, J=4 Hz), 10.19 (2H,brs), 10.40 (1H, brs)

PREPARATION EXAMPLE 8

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.07 g of benzoyl chloride and 10 ml of pyridine was stirred at roomtemperature for 2 hours. Water was poured into the reaction mixture, anda deposited precipitate was collected by filtration to obtain 0.15 g ofthe present compound (8) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.18 (3H, s), 7.48-7.69 (5H, m), 7.77(1H, s), 7.90-7.96 (3H, m), 8.22 (1H, d, J=8 Hz), 8.55 (1H, d, J=4 Hz),10.36 (1H, brs), 10.42 (1H, brs), 10.60 (1H, brs)

PREPARATION EXAMPLE 9

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.07 g of 4-morpholinecarbonyl chloride and 10 ml of pyridine wasstirred at room temperature for 2 hours. Water was poured into thereaction mixture, and a deposited precipitate was collected byfiltration to obtain 0.12 g of the present compound (9) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.15 (3H, s), 3.22-3.42 (4H, m),3.53-3.63 (4H, m), 7.44 (1H, s), 7.53 (1H, s), 7.66 (1H, dd, J=8 Hz, 4Hz), 7.77 (1H, s), 8.22 (1H, d, J=8 Hz), 8.54 (1H, d, J=4 Hz), 8.78 (1H,brs), 9.88 (1H, brs), 10.33 (1H, brs)

PREPARATION EXAMPLE 10

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.06 g of N,N-dimethylcarbamoyl chloride and 10 ml of pyridine wasstirred at room temperature for 2 hours. Water was poured into thereaction mixture, and a deposited precipitate was collected byfiltration to obtain 0.13 g of the present compound (10) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.14 (3H, s), 2.86 (6H, s), 7.42 (1H, s),7.52 (1H, s), 7.67 (1H, dd, J=8 Hz, 4 Hz), 7.82 (1H, s), 8.22 (1H, d,J=8 Hz), 8.48-8.58 (2H, m), 9.83 (1H, brs), 10.31 (1H, brs)

PREPARATION EXAMPLE 11

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.06 g of N-propyl chloroformate and 10 ml of pyridine was stirred atroom temperature for 2 hours. Water was poured into the reactionmixture, and a deposited precipitate was collected by filtration toobtain 0.24 g of the present compound (11) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 0.66-0.98 (3H, m), 1.37-1.66 (2H, m),2.16 (3H, s), 3.83-4.08 (2H, m), 7.38 (1H, s), 7.55 (1H, s), 7.66 (1H,dd, J=8 Hz, 4 Hz), 7.71 (1H, s), 8.22 (1H, d, J=8 Hz), 8.53 (1H, d, J=4Hz), 9.26 (1H, brs), 10.14 (1H, brs), 10.37 (1H, brs)

PREPARATION EXAMPLE 12

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.05 g of ethyl isocyanate and 10 ml of tetrahydrofuran was stirred atroom temperature for 2 hours. Water was poured into the reactionmixture, and a deposited precipitate was collected by filtration toobtain 0.16 g of the present compound (12) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.12 (3H, t, J=6 Hz), 2.18 (3H, s), 3.78(2H, q, J=6 Hz), 6.34 (1H, m), 7.48 (1H, s), 7.54 (1H, s), 7.65-7.69(2H, m), 7.74 (1H, brs), 8.23 (1H, d, J=8 Hz), 8.54 (1H, d, J=4 Hz),9.99 (1H, brs), 10.34 (1H, brs)

PREPARATION EXAMPLE 13

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.07 g of phenyl isocyanate and 10 ml of tetrahydrofuran was stirred atroom temperature for 2 hours. Water was poured into the reactionmixture, and a deposited precipitates were collected by filtration toobtain 0.12 g of the present compound (13) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.18 (3H, s), 6.93-7.00 (2H, m),7.21-7.31 (2H, m), 7.40-7.47 (2H, m), 7.51 (1H, s), 7.54-7.58 (1H, m),7.66 (1H, dd, J=8 Hz, 4 Hz), 7.71 (1H, s), 8.22 (1H, d, J=8 Hz), 8.53(1H, d, J=4 Hz), 8.73 (1H, brs), 10.18 (1H, brs), 10.40 (1H, brs)

PREPARATION EXAMPLE 14

A mixture of 0.24 g ofN-(2-methylaminobenzoyl)-N′-ethoxycarbonylhydrazine, 0.31 g of1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carbonylchloride and 10 ml of pyridine was stirred at room temperature for 2hours. Water was poured into the reaction mixture, and a depositedprecipitate was collected by filtration to obtain 0.20 g of the presentcompound (14) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.06-1.27 (3H, m), 3.18 (3H, s),4.01-4.16 (2H, m), 6.34 (1H, s), 7.31-7.37 (1H, m), 7.53-7.61 (3H, m),7.71 (1H, dd, J=8 Hz, 4 Hz), 8.31 (1H, d, J=8 Hz), 8.62 (1H, d, J=4 Hz),9.33 (1H, brs), 10.44 (1H, brs)

PREPARATION EXAMPLE 15

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.05 g of ethanesulfonyl chloride and 10 ml of pyridine was stirred atroom temperature for 2 hours. Water was poured into the reactionmixture, and a deposited precipitate was collected by filtration toobtain 0.14 g of the present compound (15) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.20 (3H, t, J=8 Hz), 2.18 (3H, s), 3.02(2H, q, J=8 Hz), 7.39 (1H, s), 7.57 (1H, s), 7.66 (1H, dd, J=8 Hz, 4Hz), 7.68 (1H, s), 8.22 (1H, d, J=8 Hz), 8.53 (1H, d, J=4 Hz), 9.95 (1H,brs), 10.41 (1H, brs), 10.57 (1H, brs)

PREPARATION EXAMPLE 16

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.05 g of N,N-dimethylsulfamoyl chloride and 10 ml of pyridine wasstirred at room temperature for 2 hours. Water was poured into thereaction mixture, and a deposited precipitate was collected byfiltration to obtain 0.14 g of the present compound (16) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.16 (3H, s), 2.71 (6H, s), 7.28 (1H, s),7.57 (1H, s), 7.66 (1H, dd, J=8 Hz, 4 Hz), 7.75 (1H, s), 8.22 (1H, d,J=8 Hz), 8.53 (1H, d, J=4 Hz), 9.31 (1H, brs), 10.42 (1H, brs), 10.51(1H, brs)

PREPARATION EXAMPLE 17

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,10 mL of formic acid and 5 ml of acetic anhydride prepared underice-cooling was stirred at room temperature for 2 hours. Water waspoured into the reaction mixture, and a deposited precipitate wascollected by filtration to obtain 0.02 g of the present compound (17) ofthe formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.16 (3H, s), 7.43 (1H, s), 7.56 (1H, s),7.66 (1H, dd, J=8 Hz, 4 Hz), 7.73 (1H, s), 8.05 (1H, s), 8.22 (1H, d,J=8 Hz), 8.53 (1H, d, J=4 Hz), 10.13 (1H, brs), 10.39 (1H, brs), 10.46(1H, brs)

PREPARATION EXAMPLE 18

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.05 g of propionyl chloride and 10 ml of pyridine was stirred at roomtemperature for 2 hours. Water was poured into the reaction mixture, anda deposited precipitate was collected by filtration to obtain 0.15 g ofthe present compound (18) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ(ppm): 1.04 (3H, t, J=8 Hz), 2.13 (5H, m), 7.44(1H, s), 7.55 (1H, s), 7.66 (1H, dd, J=8 Hz, 4 Hz), 7.74 (1H, s), 8.22(1H, d, J=8 Hz), 8.54 (1H, d, J=4 Hz), 9.91 (1H, brs), 10.16 (1H, brs),10.36 (1H, brs)

PREPARATION EXAMPLE 19

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.05 g of n-butyl chloroformate and 10 ml of pyridine was stirred atroom temperature for 2 hours. Water was poured into the reactionmixture, and a deposited precipitate was collected by filtration toobtain 0.19 g of the present compound (19) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 0.79-0.94 (3H, m), 1.22-1.40 (2H, m),1.46-1.62 (2H, m), 2.17 (3H, s), 3.92-4.13 (2H, m), 7.37 (1H, s), 7.56(1H, s), 7.66 (1H, dd, J=8 Hz, 4 Hz), 7.70 (1H, s), 8.22 (1H, d, J=8Hz), 8.53 (1H, d, J=4 Hz), 9.25 (1H, brs), 10.14 (1H, brs), 10.37 (1H,brs)

PREPARATION EXAMPLE 20

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.05 g of allyl chloroformate and 10 ml of pyridine was stirred at roomtemperature for 2 hours. Water was poured into the reaction mixture, anda deposited precipitate was collected by filtration to obtain 0.23 g ofthe present compound (20) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.16 (3H, s), 4.43-4.60 (2H, m), 5.21(1H, d, J=6 Hz), 5.33 (1H, d, J=8 Hz), 5.86-6.00 (1H, m), 7.39 (1H, s),7.56 (1H, s), 7.66 (1H, dd, J=8 Hz, 4 Hz), 7.70 (1H, s), 8.22 (1H, d,J=8 Hz), 8.54 (1H, d, J=4 Hz), 9.39 (1H, brs), 10.18 (1H, brs), 10.38(1H, brs)

PREPARATION EXAMPLE 21

A mixture of 0.22 g ofN-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.05 g of methyl chloroformate and 10 ml of pyridine was stirred at roomtemperature for 2 hours. Water was poured into the reaction solution,and a deposited precipitate was collected by filtration to obtain 0.09 gof the present compound (21) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.11 (3H, s), 3.06 (3H, s), 3.33 (3H, s),7.07 (1H, s), 7.45 (1H, s), 7.68 (1H, s), 7.69 (1H, dd, J=8 Hz, 4 Hz),8.24 (1H, d, J=8 Hz), 8.55 (1H, d, J=4 Hz), 9.11 (0.6H, brs), 10.20 (1H,brs), 10.54 (0.4H, brs)

PREPARATION EXAMPLE 22

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.05 g of N,N-diethylcarbamoyl chloride and 10 ml of pyridine wasstirred at room temperature for 2 hours. Water was poured into thereaction mixture, and a deposited precipitate was collected byfiltration to obtain 0.19 g of the present compound (22) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.06 (6H, t, J=6 Hz), 2.14 (3H, s), 3.26(4H, q, J=6 Hz), 7.42 (1H, s), 7.52 (1H, s), 7.68 (1H, dd, J=8 Hz, 4Hz), 7.82 (1H, s), 8.23 (1H, d, J=8 Hz), 8.48 (1H, brs), 8.53 (1H, d,J=4 Hz), 9.84 (1H, brs), 10.35 (1H, brs)

PREPARATION EXAMPLE 23

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.10 g of N-methyl-N-phenylcarbamoyl chloride and 10 ml of pyridine wasstirred at room temperature for 2 hours. Water was poured into thereaction mixture, and a deposited precipitate was collected byfiltration to obtain 0.19 g of the present compound (23) of a formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.15 (3H, s), 3.08 (3H, s), 7.10-7.45(6H, m), 7.53 (1H, s), 7.66 (1H, dd, J=8 Hz, 4 Hz), 7.76 (1H, s), 8.14(1H, brs), 8.20 (1H, d, J=8 Hz), 8.50 (1H, d, J=4 Hz), 9.97 (1H, brs),10.32 (1H, brs)

PREPARATION EXAMPLE 24

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.15 g of N,N-diphenylcarbamoyl chloride and 10 ml of pyridine wasstirred at room temperature for 2 hours. Water was poured into thereaction mixture, and a deposited precipitate was collected byfiltration to obtain 0.24 g of the present compound (24) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.15 (3H, s), 6.77 (1H, t, J=8 Hz), 6.81(1H, t, J=8 Hz), 7.05-7.39 (9H, m), 7.52 (1H, s), 7.64 (1H, dd, J=8 Hz,4 Hz), 7.72 (1H, s), 8.13 (1H, brs), 8.19 (1H, d, J=8 Hz) 8.47 (1H, d,J=4 Hz), 10.08 (1H, brs), 10.34 (1H, brs)

PREPARATION EXAMPLE 25

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.07 g of picolinoyl chloride hydrochloride and 10 ml of pyridine wasstirred at room temperature for 2 hours. Water was poured into areaction mixture, and a deposited precipitate was collected byfiltration to obtain 0.16 g of the present compound (25) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.18 (3H, s), 7.50-7.59 (2H, m),7.63-7.71 (3H, m), 7.77-7.88 (1H, m), 8.05 (1H, s), 8.06 (1H, s), 8.23(1H, d, J=8 Hz), 8.54 (1H, d, J=4 Hz), 8.70 (1H, d, J=4 Hz), 10.35-10.70(2H, m)

PREPARATION EXAMPLE 26

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.07 g of phenyl chloroformate and 10 ml of pyridine was stirred at roomtemperature for 2 hours. Water was poured into the reaction mixture, anda deposited precipitate was collected by filtration to obtain 0.16 g ofthe present compound (26) of a formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.17 (3H, s), 7.13-7.69 (9H, m), 8.22(1H, d, J=8 Hz) 8.53 (1H, d, J=4 Hz), 9.95 (1H, brs), 10.43 (1H, brs),10.45 (1H, brs)

PREPARATION EXAMPLE 27

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.04 g of acetyl chloride and 10 ml of pyridine was stirred at roomtemperature for 2 hours. Water was poured into the reaction mixture, anda deposited precipitate was collected by filtration to obtain 0.22 g ofthe present compound (27) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.89 (3H, s), 2.16 (3H, s), 7.44 (1H, s),7.55 (1H, s), 7.66 (1H, dd, J=8 Hz, 4 Hz), 7.73 (1H, s), 8.21 (1H, d,J=8 Hz), 8.54 (1H, d, J=4 Hz), 9.94 (1H, brs), 10.17 (1H, brs), 10.38(1H, brs)

PREPARATION EXAMPLE 28

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.06 g of trimethylacetyl chloride and 10 ml of pyridine was stirred atroom temperature for 2 hours. Water was poured into the reactionmixture, and a deposited precipitate was collected by filtration toobtain 0.25 g of the present compound (28) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.17 (9H, s), 2.15 (3H, s), 7.46 (1H, s),7.54 (1H, s), 7.66 (1H, dd, J=8 Hz, 4 Hz), 7.76 (1H, s), 8.23 (1H, d,J=8 Hz), 8.54 (1H, d, J=4 Hz), 9.66 (1H, brs), 10.01 (1H, brs), 10.32(1H, brs)

PREPARATION EXAMPLE 29

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.05 g of methyl chlorothiol formate of the formula:

and 10 ml of pyridine was stirred at room temperature for 2 hours. Waterwas poured into the reaction mixture, and a deposited precipitate wascollected by filtration to obtain 0.10 g of the present compound (29) ofthe formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.03-2.34 (6H, m), 7.40 (1H, s), 7.58(1H, s), 7.66 (1H, dd, J=8 Hz, 4 Hz), 7.71 (1H, s), 8.22 (1H, d, J=8Hz), 8.53 (1H, d, J=4 Hz), 9.84 (1H, brs), 10.41 (1H, brs), 10.56 (1H,brs)

PREPARATION EXAMPLE 30

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.09 g of 3-methylbenzoyl chloride and 10 ml of pyridine was stirred atroom temperature for 2 hours. Water was poured into the reactionmixture, and a deposited precipitate was collected by filteration toobtain 0.19 g of the present compound (30) of the formula:

¹H-NMR (DMSO-d₆, TMS)_(b)(ppm): 2.18 (3H, s), 2.30 (3H, s), 7.40 (1H,s), 7.55 (1H, s), 7.58 (1H, s), 7.65-7.73 (4H, m), 7.77 (1H, s), 8.23(1H, d, J=8 Hz), 8.54 (1H, d, J=4 Hz), 10.35 (1H, brs), 10.41 (1H, brs),10.54 (1H, brs)

PREPARATION EXAMPLE 31

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.09 g of 4-methoxybenzoyl chloride and 10 ml of pyridine was stirred atroom temperature for 2 hours. Water was poured into the reactionmixture, and a deposited precipitate was collected by filtration toobtain 0.09 g of the present compound (31) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.18 (3H, s), 3.83 (3H, s), 7.04 (2H, d,J=8 Hz), 7.55 (1H, s), 7.58 (1H, s), 7.69 (1H, dd, J=8 Hz, 4 Hz), 7.77(1H, s), 7.90 (2H, d, 8 Hz), 8.23 (1H, d, J=8 Hz), 8.54 (1H, d, J=4 Hz),10.28 (1H, brs), 10.41 (1H, brs), 10.45 (1H, brs)

PREPARATION EXAMPLES 32

A mixture of 0.18 g of1-(3-chloro-2-pyridinyl)-N-[2-(hydrazinocarbonyl)-6-methylphenyl]-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.06 ml of ethyl chloroformate and 1 ml of pyridine was stirred at roomtemperature for 2 hours. Water and toluene were added successively tothe reaction mixture, and the mixture was concentrated under reducedpressure. The resulting residue was mixed with methyl tert-butyl etherand water, the mixture was separated into layers, the resulting organiclayer was washed with an aqueous saturated sodium chloride solution,dried over anhydrous magnesium sulfate, and concentrated under reducedpressure. The resulting residue was subjected to silica gel columnchromatography to obtain 0.14 g of the present compound (32) of theformula:

¹H-NMR (CDCl₃, TMS)_(b)(ppm): 1.26 (3H, brm), 2.21 (3H, s), 4.18 (2H,brq, J=7 Hz), 6.88 (1H, brs), 7.17 (1H, t, J=8 Hz), 7.28-7.39 (4H, m),7.86 (1H, d, J=8 Hz), 8.05 (1H, brs), 8.43 (1H, d, J=4 Hz), 9.73 (1H,brs)

PREPARATION EXAMPLE 33

A mixture of 0.21 g ofN-[2-chloro-6-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.06 ml of ethyl chloroformate and 5 ml of pyridine was stirred at roomtemperature for 2 hours. Water was poured into the reaction mixture, andthe mixture was extracted with methyl tert-butyl ether three times. Theorganic layers were combined, washed successively with 2mol/L-hydrochloric acid, an aqueous saturated sodium bicarbonatesolution and an aqueous saturated sodium chloride solution, dried overanhydrous magnesium sulfate, and concentrated under reduced pressure.The resulting residue was subjected to silica gel column chromatographyto obtain 0.16 g of the present compound (33) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.28 (3H, t, J=7 Hz), 4.21 (2H, q, J=7 Hz),6.76 (1H, brs), 7.23-7.30 (2H, m), 7.42 (1H, dd, J=8 Hz, 4 Hz), 7.50(1H, d, J=8 Hz), 7.55 (1H, d, J=8 Hz), 7.85 (1H, brs), 7.90 (1H, dd, J=8Hz, 1Hz), 8.47 (1H, dd, J=4 Hz, 1Hz), 9.16 (1H, brs)

PREPARATION EXAMPLE 34

A mixture of 0.30 g of3-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide,0.20 ml of methyl chloroformate, 0.09 ml of triethylamine, 20 ml ofacetonitrile and 10 ml of N,N-dimethylformamide was stirred at roomtemperature for 3 hours. Water was poured into the reaction mixture, andthe mixture was extracted with methyl tert-butyl ether three times. Theorganic layers were combined, washed with an aqueous saturated sodiumchloride solution, dried with anhydrous magnesium sulfate, andconcentrated under reduced pressure. The resulting residue was subjectedto silica gel column chromatography to obtain 0.13 g of the presentcompound (34) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 2.14 (3H, s), 3.61 (3H, brs), 7.33 (1H, s),7.37 (1H, brs), 7.53 (1H, brs), 7.60 (1H, dd, J=8 Hz, 4 Hz), 8.16 (1H,dd, J=8 Hz, 1Hz), 8.49 (1H, dd, J=4 Hz, 1Hz), 9.29 (1H, brs), 10.15 (1H,brs), 10.22 (1H, brs)

PREPARATION EXAMPLE 35

A mixture of 0.30 g of3-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide,0.09 ml of ethyl chloroformate and 3 ml of pyridine was stirred at roomtemperature for 3 hours, and concentrated under reduced pressure. Waterand toluene were added to the resulting residue, the mixture wasfiltered, the resulting filter cake was mixed with methyl tert-butylether and water, and the mixture was separated into layers. The organiclayer was washed with an aqueous saturated sodium chloride solution,dried over anhydrous magnesium sulfate, and concentrated under reducedpressure. The resulting residue was subjected to silica gel columnchromatography to obtain 0.23 g of the present compound (35) of theformula:

¹H-NMR (DMSO-d₆) δ (ppm): 1.18 (3H, brm), 2.14 (3H, s), 4.06 (2H, brm),7.34 (1H, s), 7.37 (1H, brs), 7.53 (1H, s), 7.60 (1H, dd, J=8 Hz, 4 Hz),8.16 (1H, dd, J=8 Hz, 1Hz), 8.49 (1H, dd, J=4 Hz, 1Hz), 9.24 (1H, brs),10.12 (1H, brs), 10.21 (1H, brs)

PREPARATION EXAMPLES 36 AND 37

To a solution of 0.30 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-chlorophenyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidein 10 ml of acetonitrile were added 0.10 ml of methyl chloroformate and0.09 ml of triethylamine, the mixture was stirred at room temperaturefor 1 hour, and 0.10 ml of methyl chloroformate was added to themixture, followed by further stirring for 3 hours. Water was poured intothe reaction mixture, and the mixture was extracted with methyltert-butyl ether three times. The organic layers were combined, washedwith an aqueous saturated sodium chloride solution, dried over anhydrousmagnesium sulfate, and concentrated under reduced pressure. Theresulting residue was subjected to silica gel column chromatography toobtain 0.16 g of the present compound (36) and 0.16 g of the presentcompound (37) of the fromulas:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.15 (3H, s), 3.76 (6H, s), 7.23-7.27 (3H,m), 7.30-7.40 (2H, m), 7.43-7.47 (2H, m), 8.84 (1H, brs), 9.29 (1H, brs)

¹H-NMR (DMSO-d₆) δ (ppm): 2.22 (3H, s), 3.68 (3H, brs), 7.44 (1H, brs),7.53-7.72 (6H, m), 9.35 (1H, brs), 10.23 (1H, brs), 10.32 (1H, brs)

PREPARATION EXAMPLE 38

A mixture of 0.30 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-chlorophenyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,2 ml of pyridine and 0.09 ml of ethyl chloroformate was stirred at roomtemperature for 1 hour, and concentrated under reduced pressure. Waterand toluene were added to the resulting residue, and the mixture wasfiltered. The filter cake was subjected to silica gel columnchromatography to obtain 0.22 g of the present compound (38) or theformula:

¹H-NMR (DMSO-d₆) δ (ppm): 1.19 (3H, brm), 2.15 (3H, s), 4.05 (2H, brm),7.37 (1H, s), 7.49-7.66 (6H, m), 9.22 (1H, brs), 10.14 (1H, brs), 10.25(1H, brs)

PREPARATION EXAMPLE 39

A mixture of 0.18 g of1-(3-chloro-2-pyridinyl)-N-[2-(hydrazinocarbonyl)-6-methylphenyl]-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.05 ml of methyl chloroformate and 1 ml of pyridine was stirred at roomtemperature for 2 hours. Water was poured into the reaction mixture, andtoluene was added, followed by concentration under reduced pressure. Theresulting residue was mixed with methyl tert-butyl ether and water, themixture was separated into layers, and the organic layer was washed withan aqueous saturated sodium chloride solution, dried with anhydrousmagnesium sulfate, and concentrated under reduced pressure. Theresulting residue was subjected to silica gel column chromatography toobtain 0.13 g of the present compound (39) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.22 (3H, s), 3.75 (3H, brs), 6.86 (1H,brs), 7.19 (1H, t, J=8 Hz), 7.27 (1H, s), 7.34-7.40 (3H, m), 7.87 (1H,dd, J=8 Hz, 1.5 Hz), 7.97 (1H, brs), 8.44 (1H, J=4 Hz, 1Hz), 9.68 (1H,brs)

PREPARATION EXAMPLE 40

A mixture of 0.30 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide,0.09 ml of methyl chloroformate and 3 ml of pyridine was stirred at roomtemperature for 1.5 hours. Water and toluene were successively added tothe reaction mixture, followed by concentration under reduced pressure.The resulting residue was mixed with ethyl acetate and water, themixture was separated into layers, and the organic layer was washed withan aqueous saturated sodium chloride solution, dried over anhydrousmagnesium sulfate, and concentrated under reduced pressure. Theresulting residue was subjected to silica gel column chromatography toobtain 0.20 g of the present compound (40) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 2.17 (3H, s), 3.62 (3H, brs), 7.25 (1H, d, J=2Hz), 7.40 (1H, brs), 7.52 (1H, d, J=2 Hz), 7.56 (1H, dd, J=8 Hz, 4 Hz),7.86 (1H, d, J=2 Hz), 8.11 (1H, dd, J=8 Hz, 1Hz), 8.48 (1H, dd, J=4 Hz,1Hz), 9.31 (1H, brs), 10.11 (1H, brs), 10.13 (1H, brs)

PREPARATION EXAMPLE 41

According to the same manner as that of Preparation Example 5,N-[4,6-dimethyl-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (41) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.11 (3H, s), 2.29 (3H, s), 3.55-3.68(3H, m), 7.19-7.25 (2H, m), 7.66 (1H, dd, J=8 Hz, 4 Hz), 7.71 (1H, s),8.22 (1H, d, J=8 Hz), 8.53 (1H, d, J=4 Hz), 9.23 (1H, brs), 9.98 (1H,brs), 10.22 (1H, brs)

PREPARATION EXAMPLE 42

According to the same manner as that of Preparation Example 10,N-[4,6-dimethyl-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluormethyl-1H-pyrazole-5-carboxamideto obtain the present compound (42) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.13 (3H, s), 2.31 (3H, s), 2.86 (6H, s),7.14-7.27 (2H, m), 7.65-7.70 (1H, m), 7.82 (1H, s), 8.23 (1H, d, J=8Hz), 8.48 (1H, brs), 8.53 (1H, d, J=4 Hz), 9.65 (1H, brs), 10.16 (1H,brs)

PREPARATION EXAMPLE 43

According to the same manner as that of Preparation Example 5,N-[6-bromo-2-(hydrazinocarbonyl)-4-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (43) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.35 (3H, s), 3.53-3.65 (3H, m), 7.35(1H, s), 7.65 (1H, dd, J=8 Hz, 4 Hz), 7.68-7.70 (1H, m), 7.76 (1H, s),8.20 (1H, d, J=8 Hz), 8.53 (1H, d, J=4 Hz), 9.27 (1H, brs), 10.04 (1H,brs), 10.47 (1H, brs)

PREPARATION EXAMPLE 44

According to the same manner as that of Preparation Example 10,N-[6-bromo-2-(hydrazinocarbonyl)-4-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluormethyl-1H-pyrazole-5-carboxamideto obtain the present compound (44) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.34 (3H, s), 2.84 (6H, s), 7.40 (1H, s),7.62-7.70 (2H, m), 7.83 (1H, s), 8.20 (1H, d, J=8 Hz), 8.48 (1H, brs),8.51-8.56 (1H, m), 9.69 (1H, brs), 10.42 (1H, brs)

PREPARATION EXAMPLE 45

According to the same manner as that of Preparation Example 5,N-[3-chloro-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (45) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.67-3.74 (3H, m), 7.37-7.47 (2H, m),7.69-7.74 (1H, m), 7.82-7.88 (2H, m), 8.25-8.33 (1H, m), 8.57 (1H, d,J=4 Hz), 9.71 (1H, brs), 9.83 (1H, brs), 10.56 (1H, brs)

PREPARATION EXAMPLE 46

According to the same manner as that of Preparation Example 10,N-[4-chloro-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluormethyl-1H-pyrazole-5-carboxamideto obtain the present compound (46) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.90 (6H, s), 7.57 (1H, d, J=8 Hz),7.68-7.70 (1H, m), 7.73 (1H, dd, 8 Hz, 4 Hz), 7.81 (1H, s), 8.18 (1H, d,J=8 Hz), 8.29 (1H, d, J=8 Hz), 8.57 (1H, d, J=4 Hz), 8.83 (1H, brs),10.36 (1H, brs), 11.27 (1H, brs)

PREPARATION EXAMPLE 47

According to the same manner as that of Preparation Example 5,N-[4-chloro-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (47) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.64-3.71 (3H, m), 7.59 (1H, s), 7.63(1H, d, J=8 Hz), 7.72 (1H, dd, J=8 Hz, 4 Hz), 7.86 (1H, s), 8.12 (1H, d,J=8 Hz), 8.29 (1H, d, J=8 Hz), 8.58 (1H, d, J=4 Hz), 9.51 (1H, brs),10.75 (1H, brs), 11.68 (1H, brs)

PREPARATION EXAMPLE 48

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.04 g of sodium cyanate, 0.5 ml of acetic acid and 5 ml of chloroformwas stirred under ice-cooling for 4 hours. The reaction mixture wasconcentrated under reduced pressure, and the resulting residue waswashed successively with water and chloroform to obtain 0.080 g of thepresent compound (48) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.16 (3H, s), 5.97 (2H, brs), 7.52-7.54(2H, m), 7.67 (1H, dd, J=8 Hz, 4 Hz), 7.70 (1H, s), 7.76 (1H, brs), 8.22(1H, d, J=8 Hz), 8.54 (1H, d, J=4 Hz), 10.01 (1H, brs), 10.39 (1H, brs)

PREPARATION EXAMPLE 49

According to the same manner as that of Preparation Example 5 exceptthatN-[4,6-dibromo-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (49) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.40-3.70 (3H, m), 7.63-7.69 (2H, m),7.76 (1H, s), 8.16 (1H, s), 8.21 (1H, d, J=8 Hz), 8.54 (1H, d, J=4 Hz),9.35 (1H, brs), 10.23 (1H, brs), 10.63 (1H, brs)

PREPARATION EXAMPLE 50

According to the same manner as that of Preparation Example 5 exceptthatN-[4,6-diiodo-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (50) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.55-3.65 (3H, m), 7.65 (1H, dd, J=8 Hz,4 Hz), 7.75-7.82 (2H, m), 8.20 (1H, d, J=8 Hz), 8.39 (1H, s), 8.53 (1H,d, J=4 Hz), 9.31 (1H, brs), 10.14 (1H, brs), 10.59 (1H, brs)

PREPARATION EXAMPLE 51

A mixture of 0.22 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.05 g of methyl isothiocyanate and 10 ml of tetrahydrofuran was stirredat room temperature for 2 hours. Water was poured into the reactionmixture, and a deposited precipitate was collected by filtration toobtain 0.20 g of the present compound (51) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.20 (3H, s), 2.85 (3H, d, J=4 Hz), 7.57(1H, s), 7.60-7.63 (2H, m), 7.68 (1H, dd, J=8 Hz, 4 Hz), 7.72 (1H, brs),8.24 (1H, d, J=8 Hz), 8.57 (1H, d, J=4 Hz), 9.13 (1H, brs), 10.31 (1H,brs), 10.42 (1H, brs)

PREPARATION EXAMPLE 52

According to the same manner as that of Preparation Example 5 exceptthatN-[5-chloro-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (52) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.60-3.77 (3H, m), 7.40 (1H, d, J=8 Hz),7.57 (1H, s), 7.74 (1H, dd, J=8 Hz, 4 Hz), 7.85 (1H, d, J=8 Hz), 8.22(1H, s), 8.31 (1H, d, J=8 Hz), 8.59 (1H, d, J=4 Hz), 9.49 (1H, brs),10.77 (1H, brs), 12.04 (1H, brs)

PREPARATION EXAMPLE 53

According to the same manner as that of Preparation Example 5 exceptthatN-[2-(hydrazinocarbonyl)-4-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (53) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.32 (3H, s), 3.60-3.72 (3H, m), 7.37(1H, d, J=8 Hz), 7.55 (1H, s), 7.65 (1H, s), 7.73 (1H, dd, J=8 Hz, 4Hz), 8.02 (1H, d, J=8 Hz), 8.29 (1H, d, J=8 Hz), 8.57 (1H, d, J=4 Hz),9.43 (1H, brs), 10.64 (1H, brs), 11.72 (1H, brs)

PREPARATION EXAMPLE 54

According to the same manner as that of Preparation Example 10 exceptthatN-[2-(hydrazinocarbonyl)-4-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluormethyl-1H-pyrazole-5-carboxamideto obtain the present compound (54) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.31 (3H, s), 2.91 (6H, s), 7.29-7.34(1H, m), 7.48-7.51 (1H, m), 7.70-7.79 (2H, m), 8.04-8.09 (1H, m),8.26-8.33 (1H, m), 8.55-8.60 (1H, m), 8.75 (1H, brs), 10.24 (1H, brs),11.30 (1H, brs)

PREPARATION EXAMPLE 55

According to the same manner as that of Preparation Example 5 exceptthatN-[2-(hydrazinocarbonyl)-3-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (55) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.32 (3H, s), 3.62-3.75 (3H, m), 7.12(1H, d, J=8 Hz), 7.31 (1H, t, J=8 Hz), 7.61 (1H, d, J=8 Hz), 7.68-7.73(1H, m), 7.80 (1H, s), 8.27 (1H, d, J=8 Hz), 8.56 (1H, d, J=4 Hz), 9.59(1H, brs), 9.66 (1H, brs), 10.30 (1H, brs)

PREPARATION EXAMPLE 56

According to the same manner as that of Preparation Example 5 exceptthatN-[4,6-dichloro-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (56) of the formula:

¹H-NMR (DMSO-d₆, TMS)_(b)(ppm): 3.45-3.66 (3H, m), 7.51 (1H, s), 7.66(1H, dd, J=8 Hz, 4 Hz), 7.76 (1H, s), 7.94 (1H, s), 8.21 (1H, d, J=8Hz), 8.53 (1H, d, J=4 Hz), 9.37 (1H, brs), 10.27 (1H, brs), 10.64 (1H,brs)

PREPARATION EXAMPLE 57

According to the same manner as that of Preparation Example 10 exceptthatN-[4,6-dichloro-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluormethyl-1H-pyrazole-5-carboxamideto obtain the present compound (57) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.85 (6H, s), 7.58 (1H, s), 7.64-7.70(1H, m), 7.85 (1H, s), 7.90 (1H, s), 8.22 (1H, d, J=8 Hz), 8.54 (1H, d,J=4 Hz), 8.58 (1H, brs), 9.91 (1H, brs), 10.59 (1H, brs)

PREPARATION EXAMPLE 58

According to the same manner as that of Preparation Example 10 exceptthatN-[4,6-dibromo-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluormethyl-1H-pyrazole-5-carboxamideto obtain the present compound (58) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.84 (6H, s), 7.67 (1H, dd, J=8 Hz, 4Hz), 7.74 (1H, s), 7.83 (1H, s), 8.13 (1H, s), 8.21 (1H, d, J=8 Hz),8.52-8.57 (2H, m), 9.88 (1H, brs), 10.60 (1H, brs)

PREPARATION EXAMPLE 59

According to the same manner as that of Preparation Example 5 exceptthatN-[6-bromo-4-chloro-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (59) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.55-3.65 (3H, m), 7.54 (1H, s), 7.66(1H, dd, J=8 Hz, 4 Hz), 7.76 (1H, s), 8.06 (1H, s), 8.21 (1H, d, J=8Hz), 8.53 (1H, d, J=4 Hz), 9.36 (1H, brs), 10.23 (1H, brs), 10.64 (1H,brs)

PREPARATION EXAMPLE 60

According to the same manner as that of Preparation Example 10 exceptthatN-[6-bromo-4-chloro-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluormethyl-1H-pyrazole-5-carboxamideto obtain the present compound (60) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.84 (6H, s), 7.62 (1H, s), 7.67 (1H, dd,J=8 Hz, 4 Hz), 7.83 (1H, s), 8.02 (1H, s), 8.21 (1H, d, J=8 Hz),8.52-8.57 (2H, m), 9.87 (1H, brs), 10.60 (1H, brs)

PREPARATION EXAMPLE 61

According to the same manner as that of Preparation Example 10 exceptthatN-[4,6-diiodo-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluormethyl-1H-pyrazole-5-carboxamideto obtain the present compound (61) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.83 (6H, s), 7.66 (1H, dd, J=8 Hz, 4Hz), 7.82 (1H, s), 7.88 (1H, s), 8.21 (1H, d, J=8 Hz), 8.37 (1H, s),8.48 (1H, brs), 8.53 (1H, d, J=4 Hz), 9.78 (1H, brs), 10.55 (1H, brs)

PREPARATION EXAMPLE 62

According to the same manner as that of Preparation Example 10 exceptthatN-[5-chloro-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (62) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.91 (6H, s), 7.33-7.48 (1H, m),7.67-7.81 (3H, m), 8.24-8.35 (2H, m), 8.56-8.63 (1H, m), 8.80 (1H, brs),10.38 (1H, brs), 11.57 (1H, brs)

PREPARATION EXAMPLE 63

According to the same manner as that of Preparation Example 5 exceptthatN-[2-(hydrazinocarbonyl)-5-methyphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (63) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.32 (3H, s), 3.60-3.69 (3H, m), 7.09(1H, d, J=8 Hz), 7.54 (1H, s), 7.71-7.79 (2H, m), 8.06 (1H, s), 8.30(1H, d, J=8 Hz), 8.58 (1H, d, J=4 Hz), 9.41 (1H, brs), 10.64 (1H, brs),12.19 (1H, brs)

PREPARATION EXAMPLE 64

According to the same manner as that of Preparation Example 10 exceptthatN-[2-(hydrazinocarbonyl)-5-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluormethyl-1H-pyrazole-5-carboxamideto obtain the present compound (64) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.31 (3H, s), 2.90 (6H, s), 7.07 (1H, d,J=8 Hz), 7.64-7.68 (2H, m), 7.74 (1H, dd, J=8 Hz, 4 Hz), 8.07 (1H, s),8.31 (1H, d, J=8 Hz), 8.58 (1H, d, J=4 Hz), 8.67 (1H, brs), 10.28 (1H,brs), 11.82 (1H, brs)

PREPARATION EXAMPLE 65

According to the same manner as that of Preparation Example 3 exceptthat N-(2-amino-5-chloro-3-methylbenzoyl)-N′-methoxycarbonylhydrazinewas used in place of N-(2-aminobenzoyl)-N′-ethoxycarbonylhydrazine toobtain the present compound (65) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.25 (3H, s), 3.59 (3H, s), 4.13 (3H, s),7.40 (1H, s), 7.44 (1H, s), 7.59 (1H, s), 9.26 (1H, brs), 10.11 (1H,brs), 10.17 (1H, brs)

PREPARATION EXAMPLE 66

A mixture of 0.28 g ofN-[1-chloro-3-(hydrazinocarbonyl)-2-naphthyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide,0.06 g of methyl chloroformate and 10 ml of pyridine was stirred at roomtemperature for 2 hours. Water was poured into the reaction mixture, anda deposited precipitate was collected by filtration to obtain 0.08 g ofthe present compound (66) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.60-3.68 (3H, m), 7.35-7.43 (1H, m),7.60-7.85 (3H, m), 8.12-8.28 (3H, m), 8.52-8.60 (2H, m), 9.35 (1H, brs),10.32 (1H, brs), 10.76 (1H, brs)

PREPARATION EXAMPLE 67

According to the same manner as that of Preparation Example 66 exceptthatN-[1-bromo-3-(hydrazinocarbonyl)-2-naphthyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[1-chloro-3-(hydrazinocarbonyl)-2-naphthyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (67) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.58-3.69 (3H, m), 7.34-7.44 (1H, m),7.60-7.85 (3H, m), 8.10-8.28 (3H, m), 8.50-8.62 (2H, m), 9.33 (1H, brs),10.28 (1H, brs), 10.78 (1H, brs)

PREPARATION EXAMPLE 68

A mixture of 0.30 g of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-6,8-dibromo-4H-3,1-benzoxazine-4-one,0.45 g of methyl carbazate and 10 ml of N,N-dimethylformamide wasstirred at room temperature for 10 hours. Into the reaction mixture, 30ml of water was poured, and the mixture was extracted with ethyl acetatethree times. The organic layers were combined, washed with an aqueoussaturated sodium chloride solution, dried over anhydrous magnesiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel column chromatography to obtain 0.14 g ofthe present compound (68) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.44-3.66 (3H, m), 7.45 (1H, s), 7.60(1H, dd, J=8 Hz, 4 Hz), 7.65 (1H, s), 8.14-8.18 (2H, m), 8.50 (1H, d,J=4 Hz), 9.36 (1H, brs), 10.26 (1H, brs), 10.55 (1H, brs)

PREPARATION EXAMPLE 69

According to the same manner as that of Preparation Example 5 exceptthatN-[4-chloro-2-(hydrazinocarbonyl)-6-methyphenyl]-1-(2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (69) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 2.33 (3H, s), 3.63 (3H, s), 7.36 (2H, s), 7.52(1H, dd, J=8 Hz, 4 Hz), 7.58 (1H, s), 7.81 (1H, d, J=8 Hz), 8.06 (1H, t,J=8 Hz), 8.46 (1H, d, J=4 Hz), 9.33 (1H, brs), 10.19 (1H, brs), 10.34(1H, brs)

PREPARATION EXAMPLE 70

A mixture of 0.30 g of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-bromo-6-chloro-4H-3,1-benzoxazine-4-one,0.45 g of methyl carbazate and 10 ml of N,N-dimethylformamide wasstirred at room temperature for 10 hours. Into the reaction mixture, 30ml of water was poured and the mixture was extracted with ethyl acetatethree times. The organic layers were combined, washed with an aqueoussaturated sodium chloride solution, dried over anhydrous magnesiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel column chromatography to obtain 0.13 g ofthe present compound (70) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.48-3.62 (3H, m), 7.41 (1H, s),7.53-7.62 (2H, m), 8.05 (1H, s), 8.16 (1H, d, J=8 Hz), 8.50 (1H, d, J=4Hz), 9.36 (1H, brs), 10.21 (1H, brs), 10.48 (1H, brs)

PREPARATION EXAMPLE 71

A mixture of 0.30 g of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-bromo-6-methyl-4H-3,1-benzoxazine-4-one,0.45 g of methyl carbazate and 10 ml of N,N-dimethylformamide wasstirred at room temperature for 10 hours. Into the reaction mixture, 30ml of water was poured, and the mixture was extracted with ethyl acetatethree times. The organic layers were combined, washed with an aqueoussaturated sodium chloride solution, dried over anhydrous magnesiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel column chromatography to obtain 0.17 g ofthe present compound (71) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.34 (3H, s), 3.56-3.64 (3H, m),7.32-7.44 (2H, m), 7.59 (1H, dd, J=8 Hz, 4 Hz), 7.66-7.71 (1H, m), 8.15(1H, d, J=8 Hz), 8.49 (1H, d, J=4 Hz), 9.27 (1H, brs), 10.01 (1H, brs),10.31 (1H, brs)

PREPARATION EXAMPLE 72

A mixture of 0.21 g of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-chloro-4H-3,1-benzoxazine-4-one,0.9 g of methyl carbazate and 10 ml of N,N-dimethylformamide was stirredat room temperature for 10 hours. Water was poured into the reactionmixture, and this was extracted with ethyl acetate. The organic layerwas washed with water, dried over sodium sulfate, and concentrated underreduced pressure. The resulting residue was subjected to silica gelcolumn chromatography to obtain 0.10 g of the present compound (72) ofthe formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.44-3.65 (3H, m), 7.40-7.54 (3H, m),7.59 (1H, dd, J=8 Hz, 4 Hz), 7.68 (1H, d, J=8 Hz), 8.15 (1H, d, J=8 Hz),8.49 (1H, d, J=4 Hz), 9.29 (1H, brs), 10.11 (1H, brs), 10.39 (1H, brs)

PREPARATION EXAMPLE 73

According to the same manner as that of Preparation Example 5 exceptthatN-[4-chloro-2-(hydrazinocarbonyl)-6-methyphenyl]-1-phenyl-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (73) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 2.18 (3H, s), 3.61 (3H, s), 7.37 (1H, s),7.49-7.55 (7H, m), 9.31 (1H, brs), 10.22 (1H, brs), 10.30 (1H, brs)

PREPARATION EXAMPLE 74

According to the same manner as that of Preparation Example 72 exceptthat6-bromo-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-yl]-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (74) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.15 (3H, s), 3.56-3.65 (3H, m),7.47-7.55 (1H, m), 7.62-7.75 (3H, m), 8.22 (1H, d, J=8 Hz), 8.53 (1H, d,J=4 Hz), 9.31 (1H, brs), 10.17 (1H, brs), 10.38 (1H, brs)

PREPARATION EXAMPLE 75

According to the same manner as that of Preparation Example 72 exceptthat2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-yl]-6-iodo-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (75) of the formula:.

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.12 (3H, s), 3.55-3.66 (3H, m),7.63-7.72 (3H, m), 7.83 (1H, s), 8.22 (1H, d, J=8 Hz), 8.53 (1H, d, J=4Hz), 9.28 (1H, brs), 10.14 (1H, brs), 10.35 (1H, brs)

PREPARATION EXAMPLE 76

A mixture of 0.18 g ofN-[4-chloro-2-(hydrazinocarobnyl)-6-methylphenyl]-3-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxamide,45 mg of methyl chloroformate, 68 mg of pyridine and 5 ml ofacetonitrile was prepared under ice-cooling, and the mixture was stirredat room temperature for 0.5 hour. Water was poured into the reactionmixture, and the mixture was extracted with ethyl acetate. The organiclayer was washed with water, dried over anhydrous sodium sulfate, andconcentrated under reduce pressure. The resulting residue was subjectedto silica gel column chromatography to obtain 0.12 g of the presentcompound (76) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 2.13 (3H, s), 3.37-3.67 (6H, m), 7.37 (1H,brs), 7.42-7.52 (4H, m), 7.60 (1H, d, J=8 Hz), 8.13 (1H, s), 9.28-9.37(2H, m), 10.13 (1H, brs)

PREPARATION EXAMPLE 77

According to the same manner as that of Preparation Example (76) exceptthatN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-5-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-3-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxamideto obtain the present compound (77) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 2.17 (3H, s), 3.46-3.62 (3H, m), 3.94 (3H, s),7.32-7.41 (4H, m), 7.44-7.46 (1H, m), 7.50 (1H, s), 8.36 (1H, s),9.30-9.34 (2H, m), 10.17 (1H, brs)

PREPARATION EXAMPLE 78

According to the same manner as that of Preparation Example 72 exceptthat2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-6-chloro-8-methoxy-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (78) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.56-3.64 (3H, m), 3.77-3.80 (3H, m),7.12 (1H, brs), 7.32 (1H, brs), 7.38 (1H, brs), 7.59 (1H, dd, J=8 Hz, 4Hz), 8.15 (1H, d, J=8 Hz), 8.49 (1H, d, J=4 Hz), 9.28 (1H, brs), 9.95(1H, brs), 10.07 (1H, brs)

PREPARATION EXAMPLE 79

According to the same manner as that of Preparation Example 72 exceptthat2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-6-chloro-8-iodo-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (79) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.56-3.64 (3H, m), 7.43 (1H, s), 7.53(1H, s), 7.60 (1H, dd, J=8 Hz, 4 Hz), 8.12-8.19 (2H, m), 8.50 (1H, d,J=4 Hz), 9.34 (1H, brs), 10.16 (1H, brs), 10.47 (1H, brs)

PREPARATION EXAMPLE 80

According to the same manner as that of Preparation Example 72 exceptthat2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-methoxy-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (80) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.52-3.64 (3H, m), 3.74 (3H, s),7.07-7.14 (1H, m), 7.21 (1H, d, J=8 Hz), 7.31-7.42 (2H, m), 7.59 (1H,dd, J=8 Hz, 4 Hz), 8.15 (1H, d, J=8 Hz), 8.49 (1H, d, J=4 Hz), 9.21 (1H,brs), 9.87 (1H, brs), 9.92 (1H, brs)

PREPARATION EXAMPLE 81

According to the same manner as that of Preparation Example 72 exceptthat2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-trifluoromethyl-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (81) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.46-3.69 (3H, m), 7.41 (1H, s), 7.59(1H, dd, J=8 Hz, 4 Hz), 7.68 (1H, t, J=8 Hz), 7.77-7.87 (1H, m),7.90-7.97 (1H, m), 8.14 (1H, d, J=8 Hz), 8.48 (1H, d, J=4 Hz), 9.32 (1H,brs), 10.14 (1H, brs), 10.48 (1H, brs)

PREPARATION EXAMPLE 82

To a mixture of 0.25 g of3-chloro-2-(3-trifluoromethyl-1H-1,2,4-triazol-1-yl)pyridine and 5 ml oftetrahydrofuran was added dropwise 0.50 ml of a 2.0M lithiumdiisopropylamide solution in heptane/tetrahydrofuran/ethylbenzene at−78° C. and the mixture was stirred at −78° C. for 15 minutes. Carbondioxide was introduced into the mixture at such a rate that an innertemperature was maintained at −60° C. or lower and, after the mixtureturned yellow, the mixture was further stirred at −78° C. for 10minutes. The temperature of the reaction mixture was raised to roomtemperature, followed by concentration. A 2N aqueous sodium hydroxidesolution was added to adjust the pH of the aqueous layer to 10 to 12,the layers were separated, and the organic layer was extracted with a0.5N aqueous sodium hydroxide solution. The aqueous layers werecombined, and washed with chloroform, and 2N hydrochloric acid was addedso that the pH of the aqueous layer became about 3, followed byextraction with ethyl acetate three times. The organic layers werecombined, washed with an aqueous saturated sodium chloride solution,dried over magnesium sulfate, and concentrated under reduced pressure toobtain 0.13 g of crude1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-1,2,4-triazole5-carboxylic acid of the formula:

A mixture of 0.13 g of the resulting crude1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-1,2,4-triazole5-carboxylic acid and 0.10 ml of thionyl chloride was heated underreflux in 10 ml of acetonitrile for 2 hours. The reaction mixture wasallowed to cool to room temperature, and concentrated under reducedpressure, the resulting residue was dissolved in 10 ml of acetonitrile,0.11 g ofN-(2-amino-5-chloro-3-methylbenzoyl)-N′-methoxycarbonylhydrazine and0.10 ml of diisopropylethylamine were added, and the mixture was stirredat room temperature for 16 hours. Water was poured into the reactionmixture, and the mixture was extracted with ethyl acetate two times. Theorganic layers were combined, washed with an aqueous saturated sodiumchloride solution, dried over anhydrous magnesium sulfate, andconcentrated under reduced pressure. The resulting residue was subjectedto silica gel column chromatography to obtain 12 mg of the presentcompound (82) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.31 (3H, s), 3.64 (3H, s), 7.40 (1H, s),7.60 (1H, s), 7.90 (1H, brs), 8.77 (1H, d, J=7 Hz), 9.33 (1H, brs), 9.50(1H, brs), 10.27 (1H, brs), 10.44 (1H, brs)

PREPARATION EXAMPLE 83

According to the same manner as that of Preparation Example 5 exceptthatN-[4-chloro-2-(hydrazinocarbonyl)-6-methyphenyl]-1-ethyl-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (83) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 1.37 (3H, t, J=7 Hz), 2.26 (3H, s), 3.60 (3H,s), 4.55 (2H, q, J=7 Hz), 7.41 (2H, s), 7.58 (1H, s), 9.26 (1H, brs),10.12 (1H, brs), 10.18 (1H, brs)

PREPARATION EXAMPLE 84

According to the same manner as that of Preparation Example 76 exceptthat1-tert-butyl-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-5-(2-chlorophenyl)-1H-pyrazole-4-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-3-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxamideto obtain the present compound (84) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 1.39 (9H, s), 2.05 (3H, s), 3.47-3.62 (3H, m),7.36-7.53 (6H, m), 8.10 (1H, s), 9.19-9.26 (2H, m), 10.12 (1H, brs)

PREPARATION EXAMPLE 85

According to the same manner as that of Preparation Example 72 exceptthat2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-7-chloro-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (85) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.17 (3H, s), 3.60-3.65 (3H, m),7.35-7.43 (2H, m), 7.54 (1H, d, J=8 Hz), 7.61 (1H, dd, J=8 Hz, 4 Hz),8.17 (1H, d, J=8 Hz), 8.50 (1H, d, J=4 Hz), 9.28 (1H, brs), 10.14 (1H,brs), 10.41 (1H, brs)

PREPARATION EXAMPLE 86

According to the same manner as that of Preparation Example 5 exceptthatN-[4-chloro-2-(hydrazinocarbonyl)-6-methyphenyl]-1-isopropyl-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (86) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 1.43 (6H, d, J=6 Hz), 2.26 (3H, s), 3.60 (3H,s), 5.41-5.45 (1H, m), 7.35 (1H, s), 7.40 (1H, s), 7.59 (1H, s), 9.26(1H, brs), 10.10 (1H, brs), 10.17 (1H, brs)

PREPARATION EXAMPLE 87

According to the same manner as that of Preparation Example 72 exceptthat2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-5,8-dichloro-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (87) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.50-3.68 (3H, m), 7.47 (1H, s),7.52-7.65 (3H, m), 8.17 (1H, d, J=8 Hz), 8.49 (1H, d, J=4 Hz), 9.43 (1H,brs), 10.17 (1H, brs), 10.47 (1H, brs)

PREPARATION EXAMPLE 88

According to the same manner as that of Preparation Example 72 exceptthat2-[3-bromo-1-(3-chloro-2-pyridinyl)-11H-pyrazole-5-yl]-5-chloro-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (88) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.09 (3H, s), 3.51-3.68 (3H, m),7.31-7.45 (3H, m), 7.61 (1H, dd, J=8 Hz, 4 Hz), 8.19 (1H, d, J=8 Hz),8.49 (1H, d, J=4 Hz), 9.43 (1H, brs), 10.04 (1H, brs), 10.13 (1H, brs)

PREPARATION EXAMPLE 89

According to the same manner as that of Preparation Example 5 exceptthatN-[4-chloro-2-(hydrazinocarbonyl)-6-methyphenyl]-1-tert-butyl-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (89) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 1.67 (9H, s), 2.28 (3H, s), 3.64 (3H, s), 7.11(1H, s), 7.42 (1H, s), 7.55 (1H, s), 9.29 (1H, brs), 10.18 (1H, brs),10.23 (1H, brs)

PREPARATION EXAMPLE 90

According to the same manner as that of Preparation Example 5 exceptthatN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-tert-butyl-5-trifluoromethyl-1H-pyrazole-3-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (90) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 1.69 (9H, s), 2.26 (3H, s), 3.57 (3H, s), 7.43(1H, s), 7.62 (1H, d, J=2 Hz), 7.82 (1H, d, J=2 Hz), 9.30 (1H, brs),10.23 (1H, brs), 10.56 (1H, brs)

PREPARATION EXAMPLE 91

According to the same manner as that of Preparation Example 72 exceptthat2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (91) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.15 (3H, s), 3.55-3.67 (3H, m),7.25-7.45 (3H, m), 7.61 (1H, dd, J=8 Hz, 4 Hz), 7.94-7.97 (1H, m), 8.17(1H, d, J=8 Hz), 8.48-8.53 (1H, m), 9.25 (1H, brs), 10.04 (1H, brs),10.20 (1H, brs)

PREPARATION EXAMPLE 92

According to the same manner as that of Preparation Example 72 exceptthat8-bromo-2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (92) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.45-3.67 (3H, m), 7.34-7.44 (2H, m),7.53 (1H, s), 7.60 (1H, dd, J=8 Hz, 4 Hz), 7.84 (1H, d, J=8 Hz), 8.15(1H, d, J=8 Hz), 8.50 (1H, d, J=4 Hz), 9.29 (1H, brs), 10.08 (1H, brs),10.42 (1H, brs)

PREPARATION EXAMPLE 93

A mixture of 0.20 g of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide,0.05 g of methyl chloroformate and 0.07 ml of pyridine inN,N-dimethylformamide was stirred at room temperature for 8 hours. Waterwas poured into the reaction mixture, and a deposited precipitate wascollected by filtration to obtain 0.16 g of the present compound (93) ofthe formula:

¹H-NMR (DMSO-d₆) δ (ppm): 2.16 (3H, s), 3.63 (3H, s), 7.23 (1H, s), 7.41(1H, d, J=2 Hz), 7.48-7.51 (3H, m), 8.05 (1H, dd, J=8 Hz, 2 Hz), 8.43(1H, dd, J=5 Hz, 2 Hz) 9.31 (1H, brs), 9.75 (1H, brs), 10.12 (1H, brs)

PREPARATION EXAMPLE 94

A mixture of 0.26 g of3-bromo-N-[4-chloro-2-(N′-isopropylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide,0.06 ml of methyl chloroformate and 2 ml of pyridine was stirred at roomtemperature for 1.5 hours. Water was poured into the reaction mixture,and the mixture was extracted with methyl t-butyl ether three times. Theorganic layers were combined, washed successively with 1N hydrochloricacid, an aqueous saturated sodium bicarbonate solution and an aqueoussaturated sodium chloride solution, dried over anhydrous magnesiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel column chromatography to obtain 0.18 g ofthe present compound (94) of the formula:

¹H-NMR (DMSO-d₆, 80° C.) δ (ppm): 1.03 (6H, d, J=7 Hz), 2.18 (3H, s),3.53 (3H, s), 4.24 (1H, hept., J=7 Hz), 7.29 (1H, s), 7.37 (1H, d, J=2Hz), 7.49 (1H, d, J=2 Hz), 7.57 (1H, dd, J=8 Hz, 4 Hz), 8.10 (1H, dd,J=8 Hz, 1Hz), 8.45 (1H, dd, J=4 Hz, 1Hz), 9.92 (1H, s), 9.98 (1H, s)

PREPARATION EXAMPLE 95

To a mixture of 4.11 g of the present compound (34), 1.45 ml oftriethylamine and 80 ml of tetrahydrofuran was added dropwise 0.69 ml ofmethyl chloroformate under ice-cooling. After the resulting mixture wasstirred at room temperature for 1 hour, water was poured into thereaction mixture, and the mixture was extracted with ethyl acetate threetimes. The organic layers were combined, washed with an aqueoussaturated sodium chloride solution, dried over anhydrous magnesiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel column chromatography to obtain 2.66 g ofthe present compound (95) of the formula:

¹H-NMR (CDCl₃, TMS)_(b)(ppm): 2.22 (3H, s), 3.82 (6H, s), 6.99 (1H, s),7.34-7.37 (2H, m), 7.41 (1H, d, J=2 Hz), 7.88 (1H, dd, J=8 Hz, 1Hz),8.37 (1H, dd, J=4 Hz, 1Hz), 8.43 (1H, s), 9.21 (1H, s)

PREPARATION EXAMPLE 96

A mixture of 0.11 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-iodo-1H-pyrazole-5-carboxamide,0.095 ml of methyl chloroformate and 2 ml of pyridine were mixed, andthe mixture was stirred at room temperature for 2.75 hours. Water andtoluene were poured into the reaction mixture, followed by concentrationunder reduced pressure. The residue was distributed between water andethyl acetate, and the organic layer was washed with an aqueoussaturated sodium chloride solution, dried over anhydrous magnesiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel column chromatography to obtain 0.11 g ofthe present compound (96) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 2.15 (3H, s), 3.63 (3H, brs), 7.40 (2H, brs),7.54 (1H, s), 7.59 (1H, dd, J=8 Hz, 4 Hz), 8.15 (1H, d, J=8 Hz), 8.49(1H, d, J=4 Hz), 9.31 (1H, brs), 10.16 (2H, brs)

PREPARATION EXAMPLE 97

A mixture of 0.27 g of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide,0.13 ml of methyl chloroformate and 3 ml of pyridine was stirred at roomtemperature for 1.75 hours. Water and toluene were poured into thereaction mixture, followed by concentration under reduced pressure. Theresidue was distributed between water and ethyl acetate, and the organiclayer was washed with an aqueous saturated sodium chloride solution,dried over anhydrous magnesium sulfate, and concentrated under reducedpressure. The resulting residue was subjected to silica gel columnchromatography to obtain 0.24 g of the present compound (97) of theformula:

¹H-NMR (DMSO-d₆, 80° C.) δ (ppm): 2.14 (3H, s), 3.59 (3H, brs), 7.43(1H, s), 7.48 (1H, s), 7.57 (1H, dd, J=8 Hz, 4 Hz), 8.03 (1H, s), 8.12(1H, d, J=8 Hz), 8.47 (1H, d, J=4 Hz), 8.94 (1H, brs), 9.81 (1H, brs),10.11 (1H, brs)

PREPARATION EXAMPLE 98

A mixture of 0.30 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-phenyl-1H-pyrazole-5-carboxamide,0.15 ml of methyl chloroformate and 3 ml of pyridine was stirred at roomtemperature for 1.75 hours. Water and toluene were poured into thereaction mixture, followed by the concentration under reduced pressure.The residue was distributed between water and ethyl acetate, and theorganic layer was washed with an aqueous saturated sodium chloridesolution, dried over anhydrous magnesium sulfate, and concentrated underreduced pressure. The resulting residue was subjected to silica gelcolumn chromatography to obtain 0.30 g of the present compound (98) ofthe formula:

¹H-NMR (DMSO-d₆) δ (ppm): 2.19 (3H, s), 3.62 (3H, brs), 7.42-7.52 (4H,m), 7.55 (1H, brs), 7.60 (1H, dd, J=8 Hz, 4 Hz), 7.70 (1H, brs), 7.88(2H, d, J=7 Hz), 8.17 (1H, dd, J=8 Hz, 1Hz), 8.32 (1H, dd, J=4 Hz, 1Hz),9.34 (1H, brs), 10.19 (2H, brs)

PREPARATION EXAMPLE 99

A mixture of 0.27 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-methylthio-1H-pyrazole-5-carboxamide,0.14 ml of methyl chloroformate and 3 ml of pyridine was stirred at roomtemperature for 2 hours. Water and toluene were poured into the reactionmixture, followed by concentration under reduced pressure. The residuewas distributed between water and ethyl acetate, and the organic layerwas washed with an aqueous saturated sodium chloride solution, driedover anhydrous magnesium sulfate, and concentrated under reducedpressure. The resulting residue was subjected to silica gel columnchromatography to obtain 0.14 g of the present compound (99) of theformula:

¹H-NMR (DMSO-d₆) δ (ppm): 2.16 (3H, s), 2.54 (3H, s) 3.62 (3H, brs),7.20 (1H, s), 7.38 (1H, brs), 7.54-7.58 (2H, m), 8.13 (1H, dd, J=8 Hz,1Hz), 8.48 (1H, dd, J=4 Hz, 1.5 Hz), 9.32 (1H, brs), 10.11 (1H, s),10.14 (1H, s)

PREPARATION EXAMPLE 100

A mixture of 0.20 g of6-chloro-2-[1-(3-chloro-2-pyrizinyl)-3-methylsulfonyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one,0.40 g of methyl carbazate and 8 ml of N,N-dimethylformamide was stirredat room temperature for 22 hours. Water was poured into the reactionmixture, the mixture was extracted with methyl t-butyl ether threetimes. The organic layers were combined, washed successively with waterand an aqueous saturated sodium chloride solution, dried over anhydrousmagnesium sulfate, and concentrated under reduced pressure. Theresulting residue was subjected to silica gel column chromatography toobtain 0.13 g of the present compound (100) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 2.16 (3H, s), 3.39 (3H, s) 3.62 (3H, brs),7.39 (1H, brs), 7.56 (1H, s), 7.67 (1H, dd, J=8 Hz, 4 Hz), 7.78 (1H, s),8.23 (1H, dd, J=8 Hz, 1Hz), 8.54 (1H, dd, J=4 Hz, 1 Hz), 9.31 (1H, brs),10.16 (1H, brs), 10.41 (1H, brs)

PREPARATION EXAMPLE 101

A mixture of 0.10 g of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-methylsulfinyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one,0.21 g of methyl carbazate and 4 ml of N,N-dimethylformamide was stirredat room temperature for 20 hours. Water was poured into the reactionmixture, and the mixture was extracted with methyl t-butyl ether threetimes. The organic layers were combined, washed successively with waterand an aqueous saturated sodium chloride solution, dried over anhydrousmagnesium sulfate, and concentrated under reduced pressure. Theresulting residue was subjected to silica gel column chromatography toobtain 0.092 g of the present compound (101) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 2.16 (3H, s), 2.99 (3H, s) 3.62 (3H, brs),7.39 (1H, brs), 7.55 (1H, s), 7.64 (1H, dd, J=8 Hz, 4 Hz), 7.74 (1H, s),8.20 (1H, dd, J=8 Hz, 1.5 Hz), 8.52 (1H, dd, J=4 Hz, 1Hz), 9.32 (1H,brs), 10.15 (1H, brs), 10.35 (1H, brs)

PREPARATION EXAMPLE 102

A mixture 0.12 g of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-methyl-1H-pyrazole-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one,0.27 g of methyl carbazate and 4 ml of N,N-dimethylformamide was stirredat room temperature for 24 hours. Water was poured into the reactionmixture, and the mixture was extracted with methyl t-butyl ether threetimes. The organic layers were combined, washed successively with waterand an aqueous saturated sodium chloride solution, dried over anhydrousmagnesium sulfate, and concentrated under reduced pressure. Theresulting residue was subjected to silica gel column chromatography toobtain 0.10 g of the present compound (102) or the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 2.15 (3H, s), 2.31 (3H, s) 3.62 (3H, brs),7.02 (1H, s), 7.40 (1H, brs), 7.52-7.55 (2H, m), 8.11 (1H, dd, J=8 Hz,1Hz), 8.46 (1H, dd, J=4 Hz, 1Hz), 9.31 (1H, brs), 10.03 (1H, brs), 10.14(1H, brs)

PREPARATION EXAMPLE 103

According to the same manner as that of Preparation Example 10 exceptthatN-[2-(hydrazinocarbonyl)-3-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (103) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 2.29 (3H, s), 2.93 (6H, s), 7.07 (1H, d, J=8Hz), 7.27 (1H, t, J=8 Hz), 7.71 (1H, dd, J=8 Hz, 4 Hz), 7.86 (1H, d, J=8Hz), 8.11 (1H, s), 8.28 (1H, d, J=8 Hz), 8.56 (1H, d, J=4 Hz), 8.99 (1H,brs), 10.10 (1H, brs), 10.19 (1H, brs)

PREPARATION EXAMPLE 104

A mixture of 0.20 g of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-isopropyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one,0.43 g of methyl carbazate and 5 ml of N,N-dimethylformamide was stirredat room temperature for 20 hours. Water was poured into the reactionmixture, and the mixture was extracted with methyl t-butyl ether threetimes. The organic layers were combined, washed successively with waterand an aqueous saturated sodium chloride solution, dried over anhydrousmagnesium sulfate, and concentrated under reduced pressure. Theresulting residue was subjected to silica gel column chromatography toobtain 0.22 g of the present compound (104) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 1.35 (6H, d, J=7 Hz), 2.22 (3H, s), 3.08 (1H,hept., J=7 Hz), 3.68 (3H, brs), 7.17 (1H, s), 7.45 (1H, brs), 7.58-7.62(2H, m), 8.17 (1H, dd, J=8 Hz, 1Hz), 8.52 (1H, dd, J=4 Hz, 1Hz), 9.39(1H, brs), 10.09 (1H, brs), 10.20 (1H, brs)

PREPARATION EXAMPLE 105

A mixture of 0.20 g of2-[1-(3-chloro-2-pyridinyl)-3-isopropyl-1H-pyrazol-5-yl]-6,8-dibromo-4H-3,1-benzoxazine-4-one,0.34 g of methyl carbazate and 4 ml of N,N-dimethylformamide was stirredat room temperature for 17 hours. Water was poured into the reactionmixture, and the mixture was extracted with methyl t-butyl ether threetimes. The organic layers were combined, washed successively with waterand an aqueous saturated sodium chloride solution, dried over anhydrousmagnesium sulfate, and concentrated under reduced pressure. Theresulting residue was subjected to silica gel column chromatography toobtain 0.16 g of the present compound (105) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 1.27 (6H, d, J=7 Hz), 3.01 (1H, hept., J=7Hz), 3.60 (3H, brs), 7.16 (1H, s), 7.53 (1H, dd, J=8 Hz, 4 Hz), 7.64(1H, brs), 8.07 (1H, dd, J=8 Hz, 1Hz), 8.11 (1H, brs), 8.45 (1H, dd, J=4Hz, 1Hz). 9.35 (1H, brs), 10.16 (1H, brs), 10.22 (1H, brs)

PREPARATION EXAMPLE 106

According to the same manner as that of Preparation Example 95 exceptthat the present compound (59) was used in place of the present compound(34) to obtain the present compound (106) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.73 (6H, s), 7.38-7.45 (3H, m), 7.64 (1H,d, J=2 Hz), 7.89 (1H, d, J=8 Hz), 8.37 (1H, d, J=4 Hz), 8.67 (1H, brs),9.21 (1H, brs)

PREPARATION EXAMPLE 107

According to the same manner as that of Preparation Example 95 exceptthat the present compound (70) was used in place of the present compound(34) to obtain the present compound (107) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.77 (6H, s), 7.09 (1H, s), 7.36 (1H, dd,J=8 Hz, 4 Hz), 7.51 (1H, d, J=2 Hz), 7.69 (1H, d, J=2 Hz), 7.88 (1H, dd,J=8 Hz, 1Hz), 8.35 (1H, dd, J=4 Hz, 1Hz), 8.63 (1H, brs), 8.95 (1H, brs)

PREPARATION EXAMPLE 108

According to the same manner as that of Preparation Example 95 exceptthat the present compound (5) was used in place of the present compound(34) to obtain the present compound (108) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.23 (3H, s), 3.81 (6H, s), 7.24 (1H, s),7.36 (1H, d, J=2 Hz), 7.39-7.42 (2H, m), 7.91 (1H, dd, J=8 Hz, 1Hz),8.28 (1H, s), 8.40 (1H, dd, J=4 Hz, 1Hz), 9.27 (1H, s).

PREPARATION EXAMPLE 109

According to the same manner as that of Preparation Example 95 exceptthat the present compound (49) was used in place of the present compound(34) to obtain the present compound (109) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.75 (6H, s), 7.37-7.43 (2H, m), 7.63 (1H,d, J=2 Hz), 7.84 (1H, d, J=2 Hz), 7.90 (1H, dd, J=8 Hz, 1Hz), 8.38 (1H,dd, J=4 Hz, J=1 Hz), 8.57 (1H, brs), 9.17 (1H, brs).

PREPARATION EXAMPLE 110

According to the same manner as that of Preparation Example 95 exceptthat the present compound (68) was used in place of the present compound(34) to obtain the present compound (110) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.78 (6H, s), 7.08 (1H, s), 7.37 (1H, dd,J=8 Hz, 4 Hz), 7.67 (1H, d, J=2 Hz), 7.87-7.90 (2H, m), 8.35 (1H, dd,J=4 Hz, 1Hz), 8.54 (1H, brs), 8.88 (1H, brs).

PREPARATION EXAMPLE 111

According to the same manner as that of Preparation Example 95 exceptthat ethyl chloroformate was used in place of methyl chloroformate toobtain the present compound (111) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.30 (3H, t, J=7 Hz), 2.24 (3H, s), 3.82(3H, s), 4.30 (2H, q, J=7 Hz), 6.97 (1H, s), 7.34-7.38 (2H, m), 7.45(1H, s), 7.88 (1H, dd, J=8 Hz, 2 Hz), 8.27 (1H, s), 8.38 (1H, dd, J=5Hz, 2 Hz), 9.21 (1H, s).

PREPARATION EXAMPLE 112

According to the same manner as that of Preparation Example 95 exceptthat isobutyl chloroformate was used in place of methyl chloroformate toobtain the present compound (112) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 0.94 (6H, d, J=7 Hz), 1.98 (1H, hept, J=7Hz), 2.24 (3H, s), 3.82 (3H, s), 4.04 (2H, d, J=7 Hz), 6.96 (1H, s),7.34-7.37 (2H, m), 7.45 (1H, d, J=2 Hz), 7.88 (1H, dd, J=8 Hz, 2 Hz),8.29 (1H, s), 8.38 (1H, dd, J=5 Hz, 2 Hz), 9.23 (1H, s).

PREPARATION EXAMPLE 113

A mixture of 0.10 g of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-cyano-1H-pyrazole-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one,0.23 g of methyl carbazate and 4 ml of N,N-dimethylformamide was stirredat room temperature for 18 hours. Water was poured into the reactionmixture, and the mixture was extracted with methyl t-butyl ether threetimes. The organic layers were combined, washed successively with waterand an aqueous saturated sodium chloride solution, dried over anhydrousmagnesium sulfate, and concentrated under reduced pressure. Theresulting residue was subjected to silica gel column chromatography toobtain 0.090 g of the present compound (113) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 2.14 (3H, s), 3.61 (3H, brs), 7.38 (1H, brs),7.54 (1H, s), 7.67 (1H, dd, J=8 Hz, 5 Hz), 7.81 (1H, s), 8.22 (1H, d,J=8 Hz), 8.53 (1H, d, J=5 Hz), 9.29 (1H, brs), 10.16 (1H, brs), 10.44(1H, brs).

PREPARATION EXAMPLE 114

A mixture of 0.30 g of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one,0.69 g of N-methyl-N-methoxycarbonylhydrazine and 15 ml ofN,N-dimethylformamide was stirred at 60° C. for 9 hours and at 80° C.for 22 hours. Water was poured into the reaction mixture, and themixture was extracted with methyl tert-butyl ether three times. Theorganic layers were combined, washed with water and an aqueous saturatedsodium chloride solution, dried over anhydrous magnesium sulfate, andconcentrated under reduced pressure. The residue was subjected to silicagel column chromatography to obtain 0.036 g of the present compound(114) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.20 (3H, s), 3.21 (3H, s), 3.74 (3H, brs),7.05 (1H, s), 7.26-7.38 (3H, m), 7.86 (1H, dd, J=8 Hz, 2 Hz), 8.03 (1H,s), 8.42 (1H, dd, J=5 Hz, 2 Hz), 9.47 (1H, s).

PREPARATION EXAMPLE 115

A mixture of 0.60 g of3-bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide,0.41 ml of methyl chloroformate and 6 ml of pyridine was stirred at roomtemperature for 3 hours. Water was poured into the reaction mixture,followed by concentration under reduced pressure. The residue wasdistributed between water and ethyl acetate, and the organic layer waswashed with an aqueous saturated sodium chloride solution, dried overanhydrous magnesium sulfate, and concentrated under reduced pressure.The residue was subjected to silica gel column chromatography to obtain0.46 g of the present compound (115) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.04 (3H, s), 3.22 (3H, s), 3.57 (2.6H, s),3.80 (0.4H, s), 7.01 (1H, s), 7.04 (1H, s), 7.28 (1H, s), 7.40 (1H, dd,J=8 Hz, 5 Hz), 7.61 (1H, brs), 7.87 (1H, dd, J=8 Hz, 2 Hz), 8.46 (1H,dd, J=5 Hz, 2 Hz), 9.80 (1H, brs).

PREPARATION EXAMPLE 116

According to the same manner as that of Preparation Example 72 exceptthat2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-6,7-dichloro-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (116) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.25 (3H, s), 3.45-3.68 (3H, m), 7.36(1H, s), 7.57-7.65 (2H, m), 8.18 (1H, d, J=8 Hz), 8.50 (1H, d, J=4 Hz),9.36 (1H, brs), 10.24 (1H, brs), 10.49 (1H, brs).

PREPARATION EXAMPLE 117

According to the same manner as that of Preparation Example 72 exceptthat2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-methyl-6-cyano-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (117) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.20 (3H, s), 3.45-3.68 (3H, m), 7.38(1H, s), 7.61 (1H, dd, J=8 Hz, 5 Hz), 7.77 (1H, s), 7.96 (1H, s), 8.17(1H, d, J=8 Hz), 8.50 (1H, d, J=5 Hz), 9.36 (1H, brs), 10.27 (1H, brs),10.49 (1H, brs).

PREPARATION EXAMPLE 118

A mixture of 0.59 g of3,5-dibromo-2-{N-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carbonyl]-N-methylamino}benzoicacid, 2 ml of thionyl chloride and one droplet of N,N-dimethylformamidewas stirred at 80° C. for 1 hour. The reaction mixture was concentratedunder reduced pressure, 10 ml of hexane was added thereto, and themixture was further concentrated under reduced pressure. The resultingresidue, 10 ml of tetrahydrofuran, 0.10 g of methyl carbazate and 1 mlof pyridine were mixed, and the mixture was stirred at room temperaturefor 3 hours. The reaction mixture was poured into 30 ml of water, andthe mixture was extracted with ethyl acetate three times. The organiclayers were combined, washed successively with water and an aqueoussaturated sodium chloride solution, dried over anhydrous sodium sulfate,and concentrated under reduced pressure. The resulting residue wassubjected to silica gel column chromatography to obtain 0.23 g of thepresent compound (118) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.05 (1.9H, s), 3.38 (1.1H, s), 3.52-3.73(3H, m), 5.68 (0.7H, brs), 7.11 (0.3H, brs), 7.57-7.81 (2H, m),8.16-8.32 (2H, m), 8.49-8.55 (1H, m), 9.42 (1H, brs), 10.54 (1H, brs).

PREPARATION EXAMPLE 119

A mixture of 0.30 g of3-bromo-N-[4-chloro-2-(N,N′-dimethylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide,0.07 ml of methyl chloroformate and 5 ml of pyridine was stirred at roomtemperature for 1 hour. Water was poured into the reaction mixture, andthe mixture was extracted with ethyl acetate three times. The organiclayers were combined, dried over anhydrous sodium sulfate, andconcentrated under reduced pressure. The resulting residue was washedwith a mixed solvent of ethyl acetate and hexane to obtain 0.09 g of thepresent compound (119) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.10-2.24 (3H, m), 2.61-2.87 (3H, m),2.90-3.18 (3H, m), 3.45-3.74 (3H, m), 7.12-7.30 (1H, m), 7.33-7.44 (1H,m), 7.44-7.58 (1H, m), 7.58-7.66 (1H, m), 8.20 (1H, d, J=8 Hz),8.47-8.54 (1H, m), 10.10-10.50 (1H, m).

PREPARATION EXAMPLE 120

According to the same manner as that of Preparation Example 72 exceptthat2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-bromo-6-fluoro-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (120) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.42-3.69 (3H, m), 7.34 (1H, d, J=8 Hz),7.41 (1H, s), 7.60 (1H, dd, J=8 Hz, 5 Hz), 7.89 (1H, d, J=8 Hz), 8.16(1H, d, J=8 Hz), 8.50 (1H, d, J=5 Hz), 9.36 (1H, brs), 10.18 (1H, brs),10.42 (1H, brs).

PREPARATION EXAMPLE 121

According to the same manner as that of Preparation Example 72 exceptthat2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-phenyl-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (121) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.49-3.68 (3H, m), 7.24-7.67 (10H, m),8.08 (1H, d, J=8 Hz), 8.43 (1H, d, J=4 Hz), 9.29 (1H, brs), 10.08 (1H,brs), 10.19 (1H, brs).

PREPARATION EXAMPLE 122

A mixture of 0.17 g of6,8-dibromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-one,0.27 g of methyl carbazate and 20 ml of N,N-dimethylformamide wasstirred at room temperature for 2 days. Water was poured into thereaction mixture, and the mixture was extracted with ethyl acetate. Theorganic layer was washed with water, dried over sodium sulfate, andconcentrated under reduced pressure to obtain 0.15 g of the presentcompound (122) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 3.67 (3H, s), 7.36 (1H, s), 7.46 (1H, d, J=2Hz), 7.54 (1H, dd, J=8 Hz, 5 Hz), 7.70 (1H, s), 8.09 (1H, d, J=8 Hz),8.13 (1H, d, J=2 Hz), 8.48 (1H, d, J=5 Hz), 9.40 (1H, brs), 9.97 (1H,brs), 10.18 (1H, brs)

PREPARATION EXAMPLE 123

According to the same manner as that of Preparation Example 122 exceptthat8-bromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-4H-3,1-benzoxazine-4-onewas used in place of6,8-dibromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-oneto obtain the present compound (123) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 3.62 (3H, s), 7.30 (1H, s), 7.39 (1H, d, J=2Hz), 7.48 (1H, dd, J=8 Hz, 5 Hz), 7.52 (1H, s), 7.96 (1H, d, J=2 Hz),8.03 (1H, dd, J=8 Hz, 2 Hz), 8.42 (1H, dd, J=5 Hz, 2 Hz), 9.35 (1H,brs), 9.92 (1H, brs), 10.11 (1H, brs)

PREPARATION EXAMPLE 124

According to the same manner as that of Preparation Example 122 exceptthat2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-cyano-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of6,8-dibromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-yl]-4H-3,1-benzoxazine-4-oneto obtain the present compound (124) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 2.21 (3H, s), 3.64 (3H, s), 7.25 (1H, d, J=2Hz), 7.41 (1H, d, J=2 Hz), 7.49 (1H, dd, J=8 Hz, 5 Hz), 7.77 (1H, s),7.88 (1H, s), 8.04 (1H, dd, J=8 Hz, 2 Hz), 8.43 (1H, dd, J=5 Hz, 2 Hz),9.36 (1H, brs), 10.05 (1H, brs), 10.27 (1H, brs)

PREPARATION EXAMPLE 125

According to the same manner as that of Preparation Example 72,2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-ethyl-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (125) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.06-1.13 (3H, m), 2.45-2.60 (2H, m),3.55-3.70 (3H, m), 7.25-7.47 (4H, m), 7.57-7.63 (1H, m), 8.14-8.19 (1H,m), 8.46-8.53 (1H, m), 9.24 (1H, brs), 9.98 (1H, brs), 10.16 (1H, brs).

PREPARATION EXAMPLE 126

According to the same manner as that of Preparation Example 5,N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-cyclohexyl-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (126) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 1.20-1.41 (3H, m), 1.67-1.80 (5H, m),1.98-2.00 (2H, m), 2.25 (3H, s), 3.56 (3H, s), 5.00-5.08 (1H, m), 7.33(1H, s), 7.40 (1H, d, J=2 Hz), 7.55 (1H, d, J=2 Hz), 9.02 (1H, brs),9.94 (1H, brs), 10.04 (1H, brs).

PREPARATION EXAMPLE 127

According to the same manner as that of Preparation Example 93,4,5-dibromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (127) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 2.09 (3H, s), 3.63 (3H, s), 7.36 (1H, s), 7.42(1H, s), 7.49 (1H, s), 7.57 (1H, dd, J=8 Hz, 5 Hz), 8.14 (1H, d, J=8Hz), 8.50 (1H, d, J=5 Hz), 9.29 (1H, brs), 9.79 (1H, brs), 10.12 (1H,brs).

PREPARATION EXAMPLE 128

A mixture of 0.20 g of4,5-dibromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide,0.04 g of N,N-dimethylcarbamoyl chloride and 0.08 ml of pyridine inN,N-dimethylformamide was stirred at room temperature for 14 hours.Water was poured into the reaction mixture and the mixture was extractedwith ethyl acetate. The organic layer was washed with water, dried oversodium sulfate, and concentrated under reduced pressure. The resultingresidue was subjected to silica gel column chromatography to obtain 0.16g of the present compound (128) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 2.08 (3H, s), 2.88 (6H, s), 7.40 (1H, d, J=2Hz), 7.44 (1H, d, J=2 Hz), 7.52 (1H, s), 7.58 (1H, dd, J=8 Hz, 5 Hz),8.14 (1H, dd, J=8 Hz, 1Hz), 8.50 (1H, dd, J=5 Hz, 1Hz), 8.56 (1H, brs),9.75 (1H, brs), 9.81 (1H, brs).

PREPARATION EXAMPLE 129

According to the same manner as that of Preparation Example 122,2-[5-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of6,8-dibromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-oneto obtain the present compound (129) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.11 (3H, s), 3.63 (3H, s), 6.48 (1H, d,J=4 Hz), 7.24 (1H, d, J=4 Hz), 7.48 (1H, s), 7.55 (1H, dd, J=8 Hz, 5Hz), 7.95 (1H, s), 8.12 (1H, dd, J=8 Hz, 2 Hz), 8.49 (1H, dd, J=5 Hz, 2Hz), 9.31 (1H, brs), 9.74 (1H, brs), 10.13 (1H, brs)

PREPARATION EXAMPLE 130

According to the same manner as that of Preparation Example 93,N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (130) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.16 (3H, s), 3.61 (3H, s), 6.37 (1H, d,J=3 Hz), 7.12-7.18 (2H, m), 7.40 (1H, s), 7.45-7.50 (2H, m), 8.03 (1H,d, J=8 Hz), 8.42 (1H, d, J=5 Hz), 9.33 (1H, brs), 9.71 (1H, brs), 10.14(1H, brs)

PREPARATION EXAMPLE 131

According to the same manner as that of Preparation Example 10,3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-(hydrazinocarbonyl)-6-methylphenyl]-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (131) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.18 (3H, s), 2.88 (6H, s), 7.49 (1H, s),7.62 (1H, dd, J=8 Hz, 5 Hz), 7.82 (1H, s), 7.93 (1H, s), 8.19 (1H, dd,J=8 Hz, 1Hz), 8.50 (1H, dd, J=5 Hz, 1Hz), 8.63 (1H, brs), 9.93 (1H,brs), 10.42 (1H, brs)

PREPARATION EXAMPLE 132

According to the same manner as that of Preparation Example 93,4,5-dichloro-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (132) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.10 (3H, s), 3.63 (3H, s), 7.39 (2H, s),7.49 (1H, s), 7.59 (1H, dd, J=8 Hz, 5 Hz), 8.15 (1H, dd, J=8 Hz, 1Hz),8.51 (1H, dd, J=5 Hz, 1Hz), 9.30 (1H, brs), 9.82 (1H, brs), 10.12 (1H,brs)

PREPARATION EXAMPLE 133

According to the same manner as that of Preparation Example 128,4,5-dichloro-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of4,5-dibromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (133) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.10 (3H, s), 2.53 (6H, s), 7.37-7.39(2H, m), 7.51 (1H, d, J=2 Hz), 7.59 (1H, dd, J=8 Hz, 5 Hz), 8.17 (1H,dd, J=8 Hz, 2 Hz), 8.52 (1H, dd, J=5 Hz, 2 Hz), 9.31 (1H, brs), 9.82(1H, brs), 10.13 (1H, brs)

PREPARATION EXAMPLE 134

A mixture of 0.50 g of4-bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide,0.11 g of methyl chloroformate, 0.18 ml of pyridine and 5 ml ofN,N-dimethylformamide was stirred at room temperature for 3 hours. Thereaction mixture was poured into water, and extracted with ethyl acetatethree times. The organic layers were combined, washed successively withwater and an aqueous saturated sodium chloride solution, dried overanhydrous sodium sulfate, and concentrated under reduced pressure. Theresulting residue was subjected to silica gel column chromatography toobtain 0.09 g of the present compound (134) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.05-2.12 (3H, m), 3.21 (3H, s), 3.54-3.76(3H, m), 7.02 (1H, d, J=2 Hz), 7.06 (2H, s), 7.29 (1H, brs), 7.33 (1H,dd, J=8 Hz, 5 Hz), 7.80-7.86 (2H, m), 8.40 (1H, dd, J=5 Hz, 2 Hz), 8.99(1H, brs)

PREPARATION EXAMPLE 135

According to the same manner as that of Preparation Example 72,2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6,8-dichloro-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (135) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.47-3.62 (3H, m), 7.40 (1H, s), 7.51(1H, s), 7.60 (1H, dd, J=8 Hz, 5 Hz), 7.93 (1H, s), 8.16 (1H, dd, J=8Hz, 1Hz), 8.50 (1H, dd, J=5 Hz, 1Hz), 9.37 (1H, brs), 10.24 (1H, brs),10.48 (1H, brs)

PREPARATION EXAMPLE 136

A mixture of 0.25 g of4-bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide,0.06 g of N,N-dimethylcarbamoyl chloride, 0.09 ml of pyridine and 5 mlof N,N-dimethylformamide was stirred at 70° C. for 8 hours. The reactionmixture was poured into water, and a deposited precipitate was collectedby filtration. The resulting solid was washed with acetonitrile toobtain 0.10 g of the present compound (136) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.11 (3H, s), 2.65-2.85 (6H, m),3.19-3.29 (3H, m), 7.07 (1H, s), 7.14 (1H, s), 7.28 (1H, s), 7.40 (1H,s), 7.50 (1H, dd, J=8 Hz, 5 Hz), 7.60 (1H, brs), 8.06 (1H, d, J=8 Hz),8.43 (1H, d, J=5 Hz), 9.86 (1H, brs)

PREPARATION EXAMPLE 137

Under ice-cooling, 0.50 g of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide,4 ml of formic acid and 2 ml of acetic anhydride were mixed. The mixturewas stirred at room temperature for 2 hours. The reaction mixture waspoured into water, and extracted with ethyl acetate three times. Theorganic layers were combined, washed successively with water and anaqueous saturated sodium chloride solution, dried over anhydrous sodiumsulfate, and concentrated under reduced pressure. The residue was washedwith acetonitrile to obtain 0.20 g of the present compound (137) of theformula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.15 (3H, s), 7.23 (1H, s), 7.42-7.44(2H, m), 7.48-7.52 (2H, m), 8.05 (1H, d, J=7 Hz), 8.43 (1H, d, J=3 Hz),8.98 (1H, s), 9.76 (1H, s), 9.96 (1H, brs), 10.12 (1H, brs)

PREPARATION EXAMPLE 138

According to the same manner as that of Preparation Example 115,3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1H-pyrazole-5-carboxamidewas used in place of3-bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideto obtain the present compound (138) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.21 (3H, s), 3.08 (3H, s), 3.45-3.70(3H, m), 7.30-7.43 (1H, m), 7.44-7.61 (1H, m), 7.63 (1H, dd, J=8 Hz, 5Hz), 7.82-7.94 (1H, m), 8.21 (1H, d, J=8 Hz, 1Hz), 8.51 (1H, dd, J=5 Hz,1Hz), 9.21 (1H, brs), 10.24 (1H, brs)

PREPARATION EXAMPLE 139

According to the same manner as that of Preparation Example 134,4-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (139) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.21 (3H, s), 3.08 (3H, s), 3.47-3.70(3H, m), 7.18-7.30 (1H, m), 7.41-7.50 (1H, m), 7.51-7.56 (2H, m),7.80-7.90 (1H, m), 8.12 (1H, dd, J=8 Hz, 1Hz), 8.45 (1H, dd, J=5 Hz,1Hz), 9.10 (1H, brs), 9.73 (1H, brs)

PREPARATION EXAMPLE 140

According to the same manner as that of Preparation Example 66,3-bromo-N-[1-bromo-3-(hydrazinocarbonyl)-2-naphthyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamidewas used in place ofN-[1-chloro-3-(hydrazinocarbonyl)-2-naphthyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (140) of the formula:

The present compound (140)¹H-NMR (DMSO-d₆, TMS) (ppm): 3.42-3.71 (3H, m), 7.48 (1H, s), 7.58 (1H,dd, J=8 Hz, 5 Hz), 7.72 (1H, t, J=7 Hz), 7.81 (1H, t, J=7 Hz), 8.10-8.21(3H, m), 8.24 (1H, d, J=8 Hz), 8.50 (1H, d, J=5 Hz), 9.34 (1H, brs),10.26 (1H, brs), 10.64 (1H, brs)

PREPARATION EXAMPLE 141

According to the same manner as that of Preparation Example 66,4-bromo-N-[1-bromo-3-(hydrazinocarbonyl)-2-naphthyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place ofN-[1-chloro-3-(hydrazinocarbonyl)-2-naphthyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (141) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.43-3.70 (3H, m), 7.37 (1H, s),7.42-7.52 (2H, m), 7.70 (1H, t, J=7 Hz), 7.79 (1H, t, J=7 Hz), 8.03 (1H,d, J=7 Hz), 8.06-8.20 (2H, m), 8.23 (1H, d, J=8 Hz), 8.43 (1H, d, J=4Hz), 9.34 (1H, brs), 10.09 (1H, brs), 10.19 (1H, brs)

PREPARATION EXAMPLE 142

According to the same manner as that of Preparation Example 17,3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-(hydrazinocarbonyl)-6-methylphenyl]-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (142) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.16-2.34 (3H, m), 7.35-7.45 (1H, m),7.57-7.66 (1H, m), 7.76-7.88 (1H, m), 7.93-8.02 (1H, m), 8.03-8.12 (1H,m), 8.17 (1H, d, J=7 Hz), 8.50 (1H, brs), 9.55-10.03 (1H, m),10.17-10.58 (2H, m)

PREPARATION EXAMPLE 143

According to the same manner as that of Preparation Example 17,4-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-(hydrazinocarbonyl)-6-methylphenyl]-1H-pyrrole-2-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (143) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.17-2.30 (3H, m), 7.24-7.36 (1H, m),7.45-7.55 (2H, m), 7.74-7.82 (1H, m), 7.88-7.95 (1H, m), 8.03-8.09 (2H,m), 8.44 (1H, d, J=5 Hz), 10.02 (1H, brs), 10.21 (1H, brs), 10.46 (1H,brs)

PREPARATION EXAMPLE 144

According to the same manner as that of Preparation Example 119,3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-(N,N′-dimethylhydrazinocarbonyl)-6-methylphenyl]-1H-pyrazole-5-carboxamidewas used in place of3-bromo-N-[4-chloro-2-(N,N′-dimethylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideto obtain the present compound (144) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.14-2.29 (3H, m), 2.64-2.87 (3H, m),2.87-3.15 (3H, m), 3.42-3.73 (3H, m), 7.30-7.45 (1H, m), 7.54-7.81 (2H,m), 7.83-8.01 (1H, m), 8.15-8.24 (1H, m), 8.50 (1H, brs), 10.20-10.68(1H, m)

PREPARATION EXAMPLE 145

A mixture of 0.25 g of3-bromo-N-[1-bromo-3-(hydrazinocarbonyl)-2-naphthyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide,0.22 g of N,N-dimethylcarbamoyl chloride, 4 ml of acetonitrile and 1 mlof pyridine was stirred at room temperature for 2 hours, and allowed tostand at room temperature overnight. Water was poured into the reactionmixture, and the mixture was extracted with ethyl acetate three times.The organic layers were combined, washed successively with water and anaqueous saturated sodium chloride solution, dried over anhydrousmagnesium sulfate, and concentrated under reduced pressure to obtain0.20 g of the present compound (145) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.88 (6H, s), 7.54 (1H, s), 7.59 (1H, dd,J=8 Hz, 5 Hz), 7.72 (1H, t, J=7 Hz), 7.79 (1H, t, J=7 Hz), 8.09 (1H, d,J=7 Hz), 8.15 (1H, dd, J=8 Hz, 1Hz), 8.19-8.26 (2H, m), 8.50 (1H, dd,J=5.1 Hz), 8.54 (1H, brs), 9.90 (1H, brs), 10.57 (1H, brs)

PREPARATION EXAMPLE 146

According to the same manner as that of Preparation Example 145,4-bromo-N-[1-bromo-3-(hydrazinocarbonyl)-2-naphthyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of3-bromo-N-[1-bromo-3-(hydrazinocarbonyl)-2-naphthyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideto obtain the present compound (146) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.88 (6H, s), 7.37-7.44 (1H, m),7.44-7.51 (2H, m), 7.69 (1H, t, J=7 Hz), 7.77 (1H, t, J=7 Hz), 8.01-8.10(2H, m), 8.19-8.25 (2H, m), 8.43 (1H, dd, J=5 Hz, 1Hz), 8.55 (1H, brs),9.84 (1H, brs), 10.05 (1H, brs)

PREPARATION EXAMPLE 147

A mixture of 0.26 g of4-bromo-N-[4-chloro-2-(N,N′-dimethylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide,0.05 g of methyl chloroformate, 0.09 ml of pyridine and 5 ml ofN,N-dimethylformamide was stirred at room temperature for 3 hours. Thereaction mixture was poured into water, and extracted with ethyl acetatethree times. The organic layers were combined, washed successively withwater and an aqueous saturated sodium chloride solution, dried overanhydrous sodium sulfate, and concentrated under reduced pressure. Theresulting residue was subjected to silica gel column chromatography toobtain 0.20 g of the present compound (147) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.18 (3H, s), 2.88-2.98 (3H, m), 3.13-3.22(3H, m), 3.63-3.82 (3H, m), 7.01-7.12 (3H, m), 7.20 (1H, s), 7.30 (1H,d, J=5 Hz), 7.79-7.80 (1H, m), 8.37-8.38 (1H, m), 8.45-8.58 (1H, brm)

PREPARATION EXAMPLE 148

According to the same manner as that of Preparation Example 93,N-[4,6-dibromo-2-(hydrazinocarbonyl)phenyl]-4,5-dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (148) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.62 (3H, s), 7.45 (1H, s), 7.58 (1H, dd,J=8 Hz, 5 Hz), 7.63 (1H, s), 8.10 (1H, s), 8.15 (1H, dd, J=8 Hz, 2 Hz),8.51 (1H, dd, J=5 Hz, 2 Hz), 9.34 (1H, brs), 10.00 (1H, brs), 10.15 (1H,brs)

PREPARATION EXAMPLE 149

A mixture of 0.50 g of3-bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide,0.09 g of acetyl chloride, 0.09 g of pyridine and 10 ml oftetrahydrofuran was stirred at room temperature for 2 hours. Water waspoured into the reaction mixture, and the mixture was extracted withethyl acetate. The organic layer was washed with water, dried overanhydrous magnesium sulfate, and concentrated under reduced pressure.The resulting residue was washed with methyl t-butyl ether and hexane toobtain 0.48 g of the present compound (149) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.56 (3H, s), 2.01 (3H, s), 3.24 (3H, s),6.97 (2H, d, J=2 Hz), 7.39-7.42 (2H, m), 7.88 (1H, dd, J=8 Hz, 1Hz),8.39 (1H, s), 8.47 (1H, dd, J=5 Hz, 1Hz), 10.12 (1H, brs)

PREPARATION EXAMPLE 150

A mixture of 0.50 g of3-bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide,0.12 g of methyl chlorothiol formate, 0.09 g of pyridine and 10 ml oftetrahydrofuran was stirred at room temperature for 2 hours. Water waspoured into the reaction mixture, and the mixture was extracted withethyl acetate. The organic layer was washed with water, dried overanhydrous magnesium sulfate, and concentrated under reduced pressure.The resulting residue was washed with methyl t-butyl ether and hexane toobtain 0.50 g of the present compound (150) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.06 (3H, brs), 2.25 (3H, brs), 3.20 (3H,brs), 6.99-7.29 (3H, m), 7.41 (1H, dd, J=8 Hz, 5 Hz), 7.88 (1H, dd, J=8Hz, 1Hz), 8.01-8.23 (1H, brm), 8.46 (1H, d, J=5 Hz), 9.49-9.79 (1H, brm)

PREPARATION EXAMPLE 151

A mixture of 0.49 g of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-10-chloro-4H-naphtho[2,3-d][1,3]oxazine-4-one,0.90 g of methyl carbazate and 5 ml of N,N-dimethylformamide was stirredat room temperature for 2 hours. Water was poured into the reactionmixture, and the mixture was extracted with ethyl acetate three times.The organic layers were combined, washed successively with water and anaqueous saturated sodium chloride solution, dried over anhydrousmagnesium sulfate, and concentrated under reduced pressure to obtain0.31 g of the present compound (151) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.59-3.68 (3H, m), 7.47 (1H, s),7.56-7.62 (1H, m), 7.74 (1H, d, J=7 Hz), 7.80 (1H, d, J=7 Hz), 8.12-8.18(3H, m), 8.25 (1H, d, J=7 Hz), 8.50 (1H, d, J=5 Hz), 9.35 (1H, brs),10.30 (1H, brs), 10.60 (1H, brs)

PREPARATION EXAMPLE 152

According to the same manner as that of Preparation Example 151,2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-10-chloro-4H-naphtho[2,3-d][1,3]oxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-10-chloro-4H-naphtho[2,3-d][1,3]oxazine-4-oneto obtain the present compound (152) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.55-3.70 (3H, m), 7.35 (1H, s),7.43-7.51 (2H, m), 7.71 (1H, t, J=8 Hz), 7.79 (1H, t, J=8 Hz), 8.04 (1H,d, J=8 Hz), 8.12 (2H, d, J=8 Hz), 8.23 (1H, d, J=8 Hz), 8.43 (1H, d, J=5Hz), 9.35 (1H, brs), 10.06 (1H, brs), 10.24 (1H, brs)

PREPARATION EXAMPLE 153

According to the same manner as that of Preparation Example 93,4-chloro-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl))-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (153) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.17 (3H, s), 3.63 (3H, s), 7.18 (1H, d,J=2 Hz), 7.35 (1H, d, J=2 Hz), 7.39 (1H, s), 7.47 (1H, s), 7.49 (1H, dd,J=8 Hz, 5 Hz), 8.03 (1H, dd, J=8 Hz, 2 Hz), 8.42 (1H, dd, J=5 Hz, 2 Hz),9.31 (1H, brs), 9.76 (1H, brs), 10.12 (1H, brs)

PREPARATION EXAMPLE 154

A mixture of 0.52 g of3-bromo-N-[4,6-dichloro-2-(N-methylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide,0.10 g of methyl chloroformate, 0.09 g of pyridine and 7 ml oftetrahydrofuran was stirred at room temperature for 1 hour. Water waspoured into the reaction mixture, and the mixture was extracted withethyl acetate. The organic layer was washed with water, dried overanhydrous magnesium sulfate, and concentrated under reduced pressure.The resulting residue was washed with methyl t-butyl ether and hexane toobtain 0.49 g of the present compound (154) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.12-3.18 (3H, brm), 3.60-3.84 (3H, brm),7.21-7.22 (2H, m), 7.34 (1H, brs), 7.41 (1H, dd, J=8 Hz, 5 Hz), 7.51(1H, brs), 7.88 (1H, dd, J=8 Hz, 1Hz), 8.48 (1H, dd, J=5 Hz, 1Hz), 9.85(1H, brs)

PREPARATION EXAMPLE 155

According to the same manner as that of Preparation Example 154, ethylchloroformate was used in place of methyl chloroformate to obtain thepresent compound (155) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.11-1.39 (3H, m), 3.12-3.18 (3H, brm),4.06-4.25 (2H, brm), 7.08-7.22 (2H, m), 7.34 (1H, brs), 7.41 (1H, dd,J=8 Hz, 5 Hz), 7.43 (1H, brs), 7.88 (1H, dd, J=8 Hz, 1Hz), 8.49 (1H, dd,J=5 Hz, 1Hz), 9.87 (1H, brs)

PREPARATION EXAMPLE 156

A mixture of 0.50 g of3-bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideand 5 ml of formic acid was stirred at 50° C. for 1 hour. Water waspoured into the reaction mixture, and the mixture was extracted withethyl acetate. The organic layer was washed with water, dried overanhydrous magnesium sulfate, and concentrated under reduced pressure.The resulting residue was washed with t-butyl ether and hexane to obtain0.40 g of the present compound (156) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.02 (3H, s), 3.25 (3H, s), 6.99 (2H, d,J=4 Hz), 7.35 (1H, s), 7.41 (1H, dd, J=8 Hz, 5 Hz), 7.64 (1H, s), 7.88(1H, dd, J=8 Hz, 2 Hz), 8.47 (1H, dd, J=5 Hz, 2 Hz), 8.58 (1H, s), 10.08(1H, s)

PREPARATION EXAMPLE 157

According to the same manner as that of Preparation Example 93,5-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (157) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.11 (3H, s), 3.63 (3H, s), 6.54 (1H, d,J=3 Hz), 7.24 (1H, d, J=3 Hz), 7.39 (1H, s), 7.46 (1H, s), 7.54 (1H, dd,J=8 Hz, 4 Hz), 8.09 (1H, d, J=8 Hz), 8.28 (1H, d, J=4 Hz), 9.30 (1H,brs), 9.74 (1H, brs), 10.13 (1H, brs)

PREPARATION EXAMPLE 158

Under ice-cooling, 0.14 ml of methyl chloroformate was added to amixture of 0.50 g of the present compound (93), 0.26 ml of triethylamineand 15 ml of tetrahydrofuran. The mixture was stirred at roomtemperature for 5 hours. Water was poured into the reaction mixture, andthe mixture was extracted with ethyl acetate three times. The organiclayers were combined, washed successively with water and an aqueoussaturated sodium chloride solution, dried over anhydrous magnesiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel column chromatography to obtain 0.21 g ofthe present compound (158) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.22 (3H, s), 3.79 (6H, s), 7.01 (1H, d,J=2 Hz), 7.07 (1H, d, J=2 Hz), 7.30 (1H, dd, J=8 Hz, 5 Hz), 7.32 (1H,s), 7.39 (1H, s), 7.82 (1H, d, J=8 Hz), 8.33 (1H, d, J=5 Hz), 8.45 (1H,brs), 8.88 (1H, brs)

PREPARATION EXAMPLE 159

According to the same manner as that of Preparation Example (158), thepresent compound (153) was used in place of the present compound (93) toobtain the present compound (159) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.18 (3H, s), 3.73 (6H, s), 7.00-7.01 (2H,m), 7.24-7.28 (3H, m), 7.79 (1H, d, J=8 Hz), 8.29 (1H, d, J=4 Hz), 8.82(1H, brs), 9.06 (1H, brs)

PREPARATION EXAMPLE 160

Under ice-cooling, 0.50 g of3-bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide,0.12 g of N,N-dimethylcarbamoyl chloride, 0.09 g of pyridine and 20 mlof tetrahydrofuran were mixed, and the mixture was stirred at 50° C. for14 hours. To the mixture were further added 0.12 g ofN,N-dimethylcarbamoyl chloride and 0.09 g of pyridine. The mixture wasstirred at 50° C. for 9 hours. Water was poured into the reactionmixture, and the mixture was extracted with ethyl acetate. The organiclayer was washed with water, dried over anhydrous magnesium sulfate, andconcentrated under reduced pressure. The resulting residue was washedwith methyl t-butyl ether and hexane to obtain 0.15 g of the presentcompound (160) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.98 (3H, s), 2.46 (6H, s), 3.30 (3H, s),6.95 (1H, d, J=2 Hz), 7.05 (1H, d, J=2 Hz), 7.37 (1H, dd, J=8 Hz, 5 Hz),7.51 (1H, s), 7.81 (1H, s), 7.85 (1H, dd, J=8 Hz, 2 Hz), 8.45 (1H, dd,J=5 Hz, 2 Hz), 10.34 (1H, brs).

PREPARATION EXAMPLE 161

According to the same manner as that of Preparation Example 93,5-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-pyrimidinyl)-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (161) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.14 (3H, s), 3.46-3.67 (3H, m),6.08-6.50 (1H, m), 7.08-7.29 (1H, m), 7.38 (1H, s), 7.51 (1H, s),7.58-7.65 (1H, m), 8.89-8.95 (2H, m), 9.09-9.39 (1H, m), 9.74-9.90 (1H,m), 10.11 (1H, brs)

PREPARATION EXAMPLE 162

According to the same manner as that of Preparation Example 93,4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2,6-dichlorophenyl)-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (162) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.11 (3H, s), 3.46-3.68 (3H, m), 7.27(1H, s), 7.30-7.47 (3H, m), 7.50 (1H, s), 7.53-7.65 (2H, m), 9.02-9.38(1H, m), 9.71 (1H, brs), 10.13 (1H, brs)

PREPARATION EXAMPLE 163

According to the same manner as that of Preparation Example 93,4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3,5-dichloro-4-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (163) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.12 (3H, s), 3.48-3.67 (3H, m),7.33-7.40 (2H, m), 7.46 (1H, d, J=2 Hz), 7.51 (1H, d, J=2 Hz), 8.76 (2H,s), 9.31 (1H, brs), 9.82 (1H, brs), 10.14 (1H, brs)

PREPARATION EXAMPLE 164

According to the same manner as that of Preparation Example 137,4,5-dichloro-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (164) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.09-2.19 (3H, s), 7.34-7.53 (3H, m),7.59 (1H, dd, J=8 Hz, 5 Hz), 8.06 (1H, s), 8.16 (1H, d, J=8 Hz), 8.52(1H, d, J=5 Hz), 9.87 (1H, brs), 10.13 (1H, brs) 10.38 (1H, brs)

PREPARATION EXAMPLE 165

Under ice-cooling, 0.43 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2,6-dichlorophenyl)-1H-pyrrole-3-carboxamide,0.15 g of methyl chloroformate, 2 ml of pyridine and 10 ml ofacetonitrile were mixed, and the mixture was stirred for 1 hour underice-cooling. Water was poured into a reaction mixture, and the mixturewas extracted with ethyl acetate three times. The organic layers werecombined, washed successively with water and an aqueous saturated sodiumchloride solution, dried over anhydrous magnesium sulfate, andconcentrated under reduced pressure to obtain 0.16 g of the presentcompound (165) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.24 (3H, s), 3.38-3.65 (3H, m), 6.81(1H, brs), 6.96 (1H, brs), 7.33-7.61 (4H, m), 7.68-7.74 (2H, m), 9.37(1H, brs), 9.52 (1H, brs), 10.21 (1H, brs)

PREPARATION EXAMPLE 166

A mixture of 0.56 g of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6,8-dibromo-4H-3,1-benzoxazine-4-one,0.47 g of 2,4,4-trimethylsemicarbazide and 15 ml of1-methyl-2-pyrrolidone was stirred at room temperature for 22 hours.Water was poured into the reaction mixture, and the mixture wasextracted with ethyl acetate. The organic layer was washed with water,dried over anhydrous magnesium sulfate, and concentrated under reducedpressure. The resulting residue was washed with ethyl acetate to obtain0.11 g of the present compound (166) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.66 (6H, s), 2.68 (3H, s), 7.45 (1H,brs), 7.59-7.63 (2H, m), 8.15-8.17 (2H, m), 8.49 (1H, d, J=4 Hz), 10.50(1H, brs), 10.55 (1H, brs).

PREPARATION EXAMPLE 167

According to the same manner as that of Preparation Example 158, thepresent compound (132) was used in place of the present compound (93) toobtain the present compound (167) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.18 (3H, s), 3.82 (6H, s), 7.00 (1H, s),7.32 (1H, d, J=2 Hz), 7.36-7.39 (2H, m), 7.86 (1H, dd, J=8 Hz, 2 Hz),8.12 (1H, s), 8.43 (1H, dd, J=5 Hz, 2 Hz), 8.85 (1H, brs)

PREPARATION EXAMPLE 168

According to the same manner as that of Preparation Example 134,4,5-dichloro-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (168) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.02-2.11 (3H, m), 3.02-3.28 (3H, m),3.54-3.89 (3H, m), 6.95-7.15 (1H, m), 7.22-7.31 (2H, m), 7.39 (1H, dd,J=8 Hz, 5 Hz), 7.70 (1H, brs), 7.87 (1H, dd, J=8 Hz, 2 Hz), 8.47 (1H,dd, J=5 Hz, 2 Hz), 9.23 (1H, brs)

PREPARATION EXAMPLE 169

According to the same manner as that of Preparation Example 5,N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-[(2-fluoro-3-pyridinyl)methyl]-3-trifluoromethyl-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (169) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.14 (3H, s), 3.52-3.62 (3H, m), 5.85(2H, s), 7.30-7.36 (1H, m), 7.39 (1H, s), 7.51 (1H, s), 7.59 (1H, d, J=2Hz), 7.61-7.71 (1H, m), 8.19 (1H, d, J=5 Hz), 9.26 (1H, brs), 10.20 (1H,brs), 10.25 (1H, brs)

PREPARATION EXAMPLE 170

Under ice-cooling, 0.08 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-[(3-chloro-2-pyridinyl)methyl]-5-trifluoromethyl-1H-pyrazole-3-carboxamide,0.05 g of methyl chloroformate, 1 ml of pyridine and 10 ml ofacetonitrile were mixed, and the mixture was stirred for 1 hour underice-cooling. Water was poured into the reaction mixture, and the mixturewas extracted with ethyl acetate three times. The organic layers werecombined, washed successively with water and an aqueous saturated sodiumchloride solution, dried over anhydrous magnesium sulfate, andconcentrated under reduced pressure to obtain 0.06 g of the presentcompound (170) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.20 (3H, s), 3.53-3.64 (3H, m), 5.86(2H, s), 7.41-7.49 (3H, m), 7.59 (1H, s), 8.03 (1H, d, J=7 Hz), 8.44(1H, d, J=4 Hz), 9.32 (1H, brs), 9.96 (1H, brs), 10.25 (1H, brs)

PREPARATION EXAMPLE 171

According to the same manner as that of Preparation Example 93,N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-4-iodo-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (171) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.15 (3H, s), 3.63 (3H, s), 7.25 (1H, s),7.38 (1H, s), 7.40 (1H, s), 7.49 (1H, dd, J=8 Hz, 5 Hz), 7.51 (1H, s),8.05 (1H, dd, J=8 Hz, 2 Hz), 8.43 (1H, dd, J=5 Hz, 2 Hz), 9.33 (1H,brs), 9.72 (1H, brs), 10.12 (1H, brs)

PREPARATION EXAMPLE 172

According to the same manner as that of Preparation Example 158, thepresent compound (171) was used in place of the present compound (93) toobtain the present compound (172) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.19 (3H, s), 3.73 (6H, s), 7.10 (1H, d,J=1 Hz), 7.14 (1H, d, J=1 Hz), 7.25-7.31 (3H, m), 7.79 (1H, dd, J=8 Hz,2 Hz), 8.31 (1H, dd, J=5 Hz, 2 Hz), 9.20 (1H, s), 9.23 (1H, brs)

PREPARATION EXAMPLE 173

According to the same manner as that of Preparation Example 151,10-chloro-2-[4,5-dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-naphtho[2,3-d][1,3]oxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-10-chloro-4H-naphtho[2,3-d][1,3]oxazine-4-oneto obtain the present compound (173) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.60 (3H, s), 7.46-7.59 (2H, m), 7.69-7.81(2H, m), 8.11-8.23 (4H, m), 8.48-8.52 (1H, m), 9.32 (1H, brs), 10.09(1H, brs), 10.22 (1H, brs)

PREPARATION EXAMPLE 174

According to the same manner as that of Preparation Example 93,4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-chloro-3-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (174) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.15 (3H, s), 3.45-3.67 (3H, m), 7.27(1H, s), 7.36 (1H, s), 7.42 (1H, d, J=1 Hz), 7.48-7.54 (2H, m), 7.94(1H, dd, J=8 Hz, 1Hz), 8.42 (1H, dd, J=5 Hz, 1Hz), 9.29 (1H, brs), 9.73(1H, brs), 10.12 (1H, brs)

PREPARATION EXAMPLE 175

According to the same manner as that of Preparation Example 151,7-bromo-2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-10-chloro-4H-naphtho[2,3-d][1,3]oxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-10-chloro-4H-naphtho[2,3-d][1,3]oxazine-4-oneto obtain the present compound (175) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.58-3.70 (3H, m), 7.46 (1H, s), 7.59(1H, dd, J=8 Hz, 5 Hz), 7.93 (1H, d, J=9 Hz), 8.08-8.21 (3H, m),8.46-8.53 (2H, m), 9.36 (1H, brs), 10.33 (1H, brs), 10.62 (1H, brs)

PREPARATION EXAMPLE 176

According to the same manner as that of Preparation Example 151,7,10-dibromo-2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-4H-naphtho[2,3-d][1,3]oxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-10-chloro-4H-naphtho[2,3-d][1,3]oxazine-4-oneto obtain the present compound (176) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.59-3.69 (3H, m), 7.47 (1H, s),7.56-7.62 (1H, m), 7.92 (1H, d, J=9 Hz), 8.10-8.20 (3H, m), 8.45-8.54(2H, m), 9.35 (1H, brs), 10.29 (1H, brs), 10.66 (1H, brs)

PREPARATION EXAMPLE 177

According to the same manner as that of Preparation Example 93,5-chloro-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (177) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.13 (3H, s), 3.63 (3H, s), 6.42 (1H, d,J=4 Hz), 7.13 (1H, d, J=4 Hz), 7.37 (1H, s), 7.42-7.47 (2H, m), 7.50(1H, d, J=2 Hz), 7.94 (1H, td, J=8 Hz, 2 Hz), 8.50 (1H, dd, J=5 Hz, 2Hz), 9.33 (1H, brs), 9.69 (1H, brs), 10.12 (1H, brs)

PREPARATION EXAMPLE 178

According to the same manner as that of Preparation Example 134,4-bromo-N-[6-bromo-4-chloro-2-(N-methylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (178) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.15 (3H, s), 3.58 (3H, s), 7.04 (1H, d,J=2 Hz), 7.26 (1H, s), 7.35 (1H, dd, J=8 Hz, 5 Hz), 7.46 (1H, d, J=2Hz), 7.70 (1H, s), 7.82 (1H, dd, J=8 Hz, 2 Hz), 8.43 (1H, dd, J=5 Hz, 2Hz), 8.55 (1H, brs), 8.80 (1H, brs)

PREPARATION EXAMPLE 179

According to the same manner as that of Preparation Example 158, thepresent compound (173) was used in place of the present compound (93) toobtain the present compound (179) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.81 (6H, s), 7.15 (1H, s), 7.35 (1H, dd,J=8 Hz, 5 Hz), 7.52-7.63 (2H, m), 7.84 (1H, d, J=8 Hz), 7.85 (1H, d, J=8Hz), 8.04 (1H, s), 8.15 (1H, dd, J=8 Hz, 2 Hz), 8.41 (1H, dd, J=5 Hz, 2Hz), 8.46 (1H, brs), 8.68 (1H, brs)

PREPARATION EXAMPLE 180

According to the same manner as that of Preparation Example 122,6,8-dibromo-2-[4-bromo-1-(3-cyano-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-onewas used in place of6,8-dibromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-oneto obtain the present compound (180) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.62 (3H, s), 7.36 (1H, d, J=2 Hz), 7.64(1H, d, J=2 Hz), 7.64 (1H, s), 7.67 (1H, dd, J=8 Hz, 5 Hz), 8.11 (1H,s), 8.47 (1H, dd, J=8 Hz, 2 Hz), 8.74 (1H, dd, J=5 Hz, 2 Hz), 9.24 (1H,brs), 10.03 (1H, brs), 10.14 (1H, brs)

PREPARATION EXAMPLE 181

According to the same manner as that of Preparation Example 122,6,8-dibromo-2-[4-bromo-1-(3-trifluoromethyl-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-onewas used in place of6,8-dibromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-oneto obtain the present compound (181) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.62 (3H, s), 7.33 (1H, s), 7.50 (1H, s),7.63 (1H, s), 7.72 (1H, dd, J=8 Hz, 5 Hz), 8.08 (1H, s), 8.33 (1H, d,J=8 Hz), 8.74 (1H, d, J=5 Hz), 9.35 (1H, brs), 9.88 (1H, brs), 10.11(1H, brs)

PREPARATION EXAMPLE 182

According to the same manner as that of Preparation Example 93,N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-5-iodo-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (182) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.11 (3H, s), 3.63 (3H, s), 6.63 (1H, d,J=4 Hz), 7.19 (1H, d, J=4 Hz), 7.40 (1H, s), 7.43 (1H, s), 7.52 (1H, dd,J=8 Hz, 5 Hz), 8.06 (1H, dd, J=8 Hz, 2 Hz), 8.48 (1H, dd, J=5 Hz, 2 Hz),9.28 (1H, brs), 9.71 (1H, brs), 10.13 (1H, brs)

PREPARATION EXAMPLE 183

According to the same manner as that of Preparation Example 72,2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-methyl-6-nitro-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (183) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.29 (3H, s), 3.51-3.68 (3H, m),7.37-7.42 (1H, m), 7.58-7.65 (1H, m), 8.14-8.22 (2H, m), 8.32-8.39 (1H,m), 8.48-8.54 (1H, m), 9.39 (1H, brs), 10.41 (1H, brs), 10.58 (1H, brs)

PREPARATION EXAMPLE 184

To a mixture of 0.26 g of N,N′-dimethylhydrazine dihydrochloride, 2 mlof water, 0.5 g of potassium carbonate and 10 ml ofN,N-dimethylformamide was added 0.20 g of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-methyl-6-nitro-4H-3,1-benzoxazine-4-one.The resulting mixture was stirred at room temperature for 2 hours. Thereaction mixture was poured into water, and extracted with ethyl acetatethree times. The organic layers were combined, washed successively withwater and an aqueous saturated sodium chloride solution, dried overanhydrous sodium sulfate, and concentrated under reduced pressure toobtain3-bromo-1-(3-chloro-2-pyridinyl)-N-[2-(N,N′-dimethylhydrazinocarbonyl)-6-methyl-4-nitrophenyl]-1H-pyrazole-5-carboxamideof the formula:

Under ice-cooling, 0.1 g of methyl chloroformate was added to a mixtureof3-bromo-1-(3-chloro-2-pyridinyl)-N-[2-(N,N′-dimethylhydrazinocarbonyl)-6-methyl-4-nitrophenyl]-1H-pyrazole-5-carboxamide,1 ml of pyridine and 10 ml of acetonitrile, and the mixture was stirredat room temperature for 2 hours. Water was poured into the reactionmixture, and the mixture was extracted with ethyl acetate two times. Theorganic layers were combined, washed successively with water and anaqueous saturated sodium chloride solution, dried over anhydrous sodiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel column chromatography to obtain 0.07 g ofthe present compound (184) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.27-2.37 (3H, m), 2.70-2.88 (3H, m),2.88-3.11 (3H, m), 3.45-3.74 (3H, m), 7.38-7.46 (1H, m), 7.63 (1H, dd,J=8 Hz, 5 Hz), 7.92-8.04 (1H, m), 8.21 (1H, dd, J=8 Hz, 1Hz), 8.24-8.34(1H, m), 8.51 (1H, dd, J=5 Hz, 1Hz), 10.40-10.75 (1H, m)

PREPARATION EXAMPLE 185

According to the same manner as that of Preparation Example 122,6,8-dibromo-2-[4-bromo-1-(3-nitro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-onewas used in place of6,8-dibromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-oneto obtain the present compound (185) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.61 (3H, s), 7.36 (1H, s), 7.57 (1H, d,J=2 Hz), 7.62 (1H, s), 7.78 (1H, dd, J=8 Hz, 5 Hz), 8.10 (1H, d, J=2Hz), 8.61 (1H, dd, J=8 Hz, 2 Hz), 8.79 (1H, dd, J=5 Hz, 2 Hz), 9.24 (1H,brs), 9.95 (1H, brs), 10.12 (1H, brs)

PREPARATION EXAMPLE 186

According to the same manner as that of Preparation Example 122,6,8-dibromo-2-[4-bromo-1-(3-bromo-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-onewas used in place of6,8-dibromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-oneto obtain the present compound (186) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.61 (3H, s), 7.32 (1H, s), 7.40 (1H, dd,J=8 Hz, 5 Hz), 7.42 (1H, s), 7.63 (1H, s), 8.10 (1H, s), 8.17 (1H, d,J=8 Hz), 8.46 (1H, d, J=5 Hz), 9.36 (1H, brs), 9.90 (1H, brs), 10.16(1H, brs)

PREPARATION EXAMPLE 187

According to the same manner as that of Preparation Example 93,4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-4-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (187) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.16 (3H, s), 3.41-3.68 (3H, m), 7.29(1H, brs), 7.33-7.40 (1H, m), 7.43 (1H, d, J=2 Hz), 7.52 (1H, d, J=2Hz), 7.55 (1H, d, J=5 Hz), 8.59 (1H, d, J=5 Hz), 8.72 (1H, brs), 9.30(1H, brs), 9.78 (1H, brs), 10.15 (1H, brs)

PREPARATION EXAMPLE 188

According to the same manner as that of Preparation Example 72,2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (188) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.68 (3H, brs), 7.23 (1H, brs), 7.62 (1H,dd, J=9 Hz, 2 Hz), 7.67 (1H, dd, J=8 Hz, 5 Hz), 7.88 (1H, s), 8.18 (1H,d, J=9 Hz), 8.25 (1H, dd, J=8 Hz, 1Hz), 8.54 (1H, dd, J=5 Hz, 1Hz), 9.49(1H, brs), 10.78 (1H, brs), 11.77 (1H, brs)

PREPARATION EXAMPLE 189

According to the same manner as that of Preparation Example 115,3-bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamidewas used in place of3-bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideto obtain the present compound (189) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.07 (3H, s), 3.51 (3H, brs), 7.29 (2H,brs), 7.47-7.54 (2H, m), 7.65 (1H, dd, J=8 Hz, 5 Hz), 8.22 (1H, dd, J=8Hz, 1Hz), 8.52 (1H, dd, J=5 Hz, 1Hz), 9.55 (1H, brs), 10.14 (1H, brs)

PREPARATION EXAMPLE 190

According to the same manner as that of Preparation Example 119,3-bromo-N-[4-chloro-2-(N,N′-dimethylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamidewas used in place of3-bromo-N-[4-chloro-2-(N,N′-dimethylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideto obtain the present compound (190) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.83-3.07 (6H, m), 3.52-3.70 (3H, m),7.29-7.60 (4H, m), 7.64 (1H, dd, J=8 Hz, 5 Hz), 8.22 (1H, dd, J=8 Hz, 2Hz), 8.51 (1H, dd, J=5 Hz, 2 Hz), 10.53-10.68 (1H, brm).

PREPARATION EXAMPLE 191

According to the same manner as that of Preparation Example 93,4,5-dichloro-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (191) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.13 (3H, s), 3.63 (3H, s), 7.24 (1H, s),7.35 (1H, s), 7.49-7.51 (3H, m), 7.97 (1H, td, J=8 Hz, 2 Hz), 8.52 (1H,dd, J=6 Hz, 2 Hz), 9.31 (1H, brs), 9.78 (1H, brs), 10.12 (1H, brs)

PREPARATION EXAMPLE 192

According to the same manner as that of Preparation Example 93,3,5-dichloro-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (192) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.09 (3H, s), 3.68 (3H, s), 6.69 (1H, s),7.42 (1H, s), 7.48-7.60 (3H, m), 7.94-8.01 (1H, m), 8.51 (1H, d, J=5Hz), 9.37 (1H, brs), 9.71 (1H, brs), 10.33 (1H, brs)

PREPARATION EXAMPLE 193

According to the same manner as that of Preparation Example 93,4-bromo-N-[4,6-dibromo-2-(hydrazinocarbonyl)phenyl]-5-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (193) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.62 (3H, s), 7.47 (1H, s), 7.58 (1H, dd,J=8 Hz, 5 Hz), 7.63 (1H, s), 8.10 (1H, s), 8.15 (1H, d, J=8 Hz), 8.51(1H, d, J=5 Hz), 9.34 (1H, brs), 10.00 (1H, brs), 10.15 (1H, brs)

PREPARATION EXAMPLE 194

According to the same manner as that of Preparation Example 128,4-bromo-N-[4,6-dibromo-2-(hydrazinocarbonyl)phenyl]-5-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of4,5-dibromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (194) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.85 (6H, s), 7.53 (1H, s), 7.59 (1H, dd,J=8 Hz, 5 Hz), 7.70 (1H, s), 8.06 (1H, s), 8.16 (1H, d, J=8 Hz), 8.51(1H, d, J=5 Hz), 8.56 (1H, brs), 9.82 (1H, brs), 9.97 (1H, brs)

PREPARATION EXAMPLE 195

A mixture of 0.59 g of3-bromo-N-[4,6-dibromo-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide,0.23 g of propargyl chloroformate, 0.16 g of pyridine and 2 ml ofacetonitrile was stirred at room temperature for 1 hour. Water waspoured into the reaction mixture, and the mixture was extracted withethyl acetate. The organic layer was washed with water, dried oversodium sulfate, and concentrated under reduced pressure. The resultingresidue was washed with ethyl acetate to obtain 0.22 g of the presentcompound (195) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.56 (1H, s), 4.71 (2H, s), 7.41 (1H, s),7.60 (1H, dd, J=8 Hz, 5 Hz), 7.66 (1H, s), 8.14-8.16 (2H, m), 8.50 (1H,dd, J=5 Hz, 1Hz), 9.60 (1H, brs), 10.29 (1H, brs), 10.50 (1H, brs).

PREPARATION EXAMPLE 196

According to the same manner as that of Preparation Example 34,propargyl chloroformate was used in place of methyl chloroformate toobtain the present compound (196) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.15 (3H, s), 3.56 (1H, brs), 4.72 (2H,s), 7.35 (1H, s), 7.39 (1H, brs), 7.55 (1H, s), 7.61 (1H, dd, J=8 Hz, 5Hz), 8.17 (1H, dd, J=8 Hz, 1Hz), 8.50 (1H, dd, J=5 Hz, 1Hz), 9.55 (1H,s), 10.23-10.26 (2H, brm).

PREPARATION EXAMPLE 197

According to the same manner as that of Preparation Example 10,3-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamidewas used in place ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideto obtain the present compound (197) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.20 (3H, s), 2.93 (6H, s), 7.50-7.52(2H, m), 7.58 (1H, brs), 7.67 (1H, dd, J=8 Hz, 5 Hz), 8.24 (1H, d, J=8Hz), 8.56 (1H, d, J=5 Hz), 8.60 (1H, s), 9.89 (1H, brs), 10.23 (1H, brs)

PREPARATION EXAMPLE 198

To a mixture of 0.20 g of the present compound (197), 0.10 ml oftriethylamine and 5 ml of tetrahydrofuran was added dropwise 0.040 ml ofmethyl chloroformate under ice-cooling. The mixture was stirred at roomtemperature for 2.5 hours. Water was poured into the reaction mixture,and the mixture was extracted with ethyl acetate three times. Theorganic layers were combined, washed with water and an aqueous saturatedsodium chloride solution, dried over anhydrous magnesium sulfate, andconcentrated under reduced pressure. The resulting residue was subjectedto silica gel column chromatography to 0.13 g of the present compound(198) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.22 (3H, s), 3.05 (3H, brs), 3.15 (3H,brs), 3.76 (3H, s), 6.99 (1H, s), 7.35-7.38 (2H, m), 7.44 (1H, s), 7.86(1H, d, J=8 Hz), 8.39 (1H, s), 8.46 (1H, d, J=5 Hz), 9.40 (1H, s)

PREPARATION EXAMPLE 199

A mixture of 1.0 g of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one,1.33 g of formic hydrazide and 40 ml of N,N-dimethylformamide wasstirred at 50° C. for 3.5 hours, and at 70° C. for 7 hours. The reactionmixture was allowed to cool to room temperature, and thereto water waspoured. The mixture was extracted with methyl tert-butyl ether. Theorganic layer was washed with water and an aqueous saturated sodiumchloride solution, dried over anhydrous magnesium sulfate, andconcentrated under reduced pressure. The resulting residue was subjectedto silica gel column chromatography to obtain 0.36 g of the presentcompound (199) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.10-2.21 (3.0H, m), 7.25-7.62 (4.7H, m),7.79-7.81 (0.2H, m), 8.05 (0.3H, s), 8.16 (1.0H, d, J=8 Hz), 8.49 (1.0H,d, J=5 Hz), 9.48-9.55 (0.7H, m), 10.05-10.45 (2.1H, m)

PREPARATION EXAMPLE 200

To a mixture of 0.20 g of the present compound (115), 0.14 ml oftriethylamine and 10 ml of acetonitrile was added 0.12 ml of methylchloroformate at room temperature. The resulting mixture was stirred atroom temperature for 18 hours. Water was poured into the reactionmixture, and the mixture was extracted with ethyl acetate three times.The organic layers were combined, washed successively with water and anaqueous saturated sodium chloride solution, dried over anhydrousmagnesium sulfate, and concentrated under reduced pressure. Theresulting residue was subjected to silica gel column chromatography toobtain 0.010 g of the present compound (200) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.21 (3H, s), 3.23 (3H, s), 3.89 (6H, brs),6.46 (1H, s), 7.08 (1H, s), 7.30 (1H, s), 7.43 (1H, dd, J=8 Hz, 5 Hz),8.92 (1H, d, J=8 Hz), 8.51 (1H, d, J=5 Hz), 9.21 (1H, s)

PREPARATION EXAMPLE 201

According to the same manner as that of Preparation Example 158, thatthe present compound (122) was used in place of the present compound(93) to obtain the present compound (201) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.74 (6H, s), 7.08 (2H, s), 7.30 (1H, dd,J=8 Hz, 5 Hz), 7.66 (1H, s), 7.82 (1H, d, J=8 Hz), 7.86 (1H, s), 8.28(1H, brs), 8.32 (1H, d, J=5 Hz), 8.60 (1H, brs)

PREPARATION EXAMPLE 202

According to the same manner as that of Preparation Example 134,4-bromo-N-[4,6-dibromo-2-(N-methylhydrazinocarbonyl)phenyl]-1-(3-chloro-3-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (202) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.05 (0.5H, brs), 3.13 (2.5H, s), 3.59(2.5H, s), 3.82 (0.5H, brs), 7.05 (1.0H, d, J=2 Hz), 7.21 (1.0H, s),7.35 (1.3H, dd, J=8 Hz, 5 Hz), 7.42 (1.0H, s), 7.65 (2.0H, s), 7.82(1.0H, d, J=8 Hz), 8.43 (1.0H, dd, J=5H, 2 Hz), 8.57 (0.7H, s)

PREPARATION EXAMPLE 203

According to the same manner as that of Preparation Example 115,3-bromo-N-[4,6-dibromo-2-(N-methylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamidewas used in place of3-bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideto obtain the present compound (203) of the formula:

¹H-NMR (100° C., DMSO-d₆, TMS) δ (ppm): 2.96 (3H, s), 3.04 (3H, brs),7.30 (1H, s), 7.38 (1H, s), 7.58 (1H, dd, J=8 Hz, 5 Hz), 7.96 (1H, s),8.11 (1H, d, J=8 Hz), 8.47 (1H, d, J=5 Hz), 8.68 (1H, brs), 10.08 (1H,brs)

PREPARATION EXAMPLE 204

A mixture of 0.30 g of3-bromo-N-[4,6-dibromo-2-(N,N′-dimethylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide,0.15 ml of methyl chloroformate and 3 ml of pyridine was stirred at roomtemperature for 2.5 hours. Then, 0.08 ml of methyl chloroformate wasadded thereto, and the mixture was stirred for 1 hour. Then, 0.08 ml ofmethyl chloroformate was added thereto, and the mixture was furtherstirred for 0.5 hour. Water was poured into the reaction mixture, andthe mixture was extracted with ethyl acetate. The organic layer wasdried over anhydrous magnesium sulfate, and concentrated under reducedpressure. The resulting residue was subjected to silica gel columnchromatography to obtain 0.24 g of the present compound (204) of theformula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.71 (1.4H, s), 2.83 (1.6H, s), 2.94(1.5H, s), 3.06 (1.5H, s), 3.35-3.70 (3.0H, m), 7.41 (0.5H, s), 7.45(0.6H, s), 7.47 (0.6H, s), 7.60-7.64 (1.3H, m), 8.07 (0.5H, d, J=2 Hz),8.13 (0.5H, s), 8.18 (1.0H, d, J=8 Hz), 8.50 (1.0H, m), 10.52 (0.5H, s),10.67 (0.5H, s)

PREPARATION EXAMPLE 205

According to the same manner as that of Preparation Example 147,4-bromo-N-[4,6-dibromo-2-(N,N′-dimethylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(N,N′-dimethylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (205) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.73 (1.4H, s), 2.82 (1.8H, s), 2.89(1.3H, s), 3.06 (1.5H, s), 3.35-3.70 (3.0H, m), 7.32 (0.5H, s),7.34-7.38 (0.6H, m), 7.43 (0.5H, s), 7.48-7.53 (2.4H, m), 8.03 (0.4H, d,J=2 Hz), 8.07-8.10 (1.6H, m), 8.43-8.45 (1.0H, m), 9.93 (0.5H, s), 10.07(0.5H, s)

PREPARATION EXAMPLE 206

According to the same manner as that of Preparation Example 136,4-bromo-N-[4,6-dibromo-2-(N-methylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamidewas used in place of4-bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideto obtain the present compound (206) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.47 (6H, s), 3.29 (3H, s), 7.04 (1H, d,J=2 Hz), 7.31 (1H, dd, J=8 Hz, 5 Hz), 7.43 (1H, d, J=2 Hz), 7.51 (1H, d,J=2 Hz), 7.53 (1H, d, J=2 Hz), 7.80 (1H, dd, J=8 Hz, 2 Hz), 8.09 (1H,s), 8.41 (1H, dd, J=5 Hz, 2 Hz), 9.67 (1H, s)

PREPARATION EXAMPLE 207

According to the same manner as that of Preparation Example 199,6,8-dibromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain the present compound (207) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.31 (0.6H, s), 7.38 (0.3H, s), 7.44(0.6H, d, J=2 Hz), 7.47-7.52 (1.5H, m), 7.65-7.75 (1.3H, m), 8.03-8.12(2.7H, m), 8.43 (1.0H, dd, J=5 Hz, 2 Hz), 9.49-9.52 (0.3H, m), 9.94-9.99(0.4H, m), 10.17 (1.0H, s), 10.39-10.44 (1.0H, m)

PREPARATION EXAMPLE 208

According to the same manner as that of Preparation Example 199,2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6,8-dibromo-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain the present compound (208) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.41 (0.7H, s), 7.45 (0.3H, s), 7.58-7.63(1.0H, m), 7.69-7.73 (1.0H, m), 7.77-7.79 (0.4H, m), 8.04 (0.6H, s),8.13-8.18 (2.0H, m), 8.49-8.51 (1.0H, m), 9.55-9.58 (0.4H, m), 10.18(0.6H, s), 10.45-10.60 (2.0H, m)

PREPARATION EXAMPLE 209

A mixture of 0.30 g of6,8-dibromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-one,0.28 g of N-methyl-N-methoxycarbonylhydrazine and 15 ml ofN,N-dimethylformamide was stirred at 80° C. for 35 hours, and thenallowed to cool to room temperature. Water was poured into the reactionmixture, and the mixture was extracted with methyl tert-butyl ether. Theorganic layer was washed successively with water and an aqueoussaturated sodium chloride solution, dried over anhydrous magnesiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel column chromatography to obtain 0.18 g ofthe present compound (209) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.84 (3H, s), 3.45-3.70 (3H, brm), 7.38(1H, brs), 7.47 (1H, d, J=2 Hz), 7.50 (1H, dd, J=8 Hz, 5 Hz), 7.54 (1H,d, J=2 Hz), 8.05 (1H, dd, J=8 Hz, 2 Hz), 8.12 (1H, d, J=2 Hz), 8.41 (1H,dd, J=5 Hz, 2 Hz), 9.95 (1H, s), 10.50 (1H, s)

PREPARATION EXAMPLE 210

A mixture of 0.16 g of4-bromo-N-[4,6-dibromo-2-(N,N′-dimethylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide,0.12 ml of N,N-dimethylcarbamoyl chloride and 0.2 ml of pyridine wasstirred at 80° C. for 5 hours and then allowed to cool to roomtemperature. Water was poured into the reaction mixture, and the mixturewas extracted with ethyl acetate. The organic layer was washedsuccessively with water and an aqueous saturated sodium chloridesolution, dried over anhydrous magnesium sulfate, and concentrated underreduced pressure. The resulting residue was subjected to silica gelcolumn chromatography to obtain 0.15 g of the present compound (210) ofthe formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.44 (4.5H, s), 2.58 (3.0H, s), 2.74(1.5H, brs), 2.78 (1.0H, s), 3.12 (2.0H, s), 7.14 (0.7H, d, J=2 Hz),7.32 (0.7H, d, J=2 Hz), 7.38 (0.3H, s), 7.47-7.54 (2.3H, m), 8.00 (0.7H,d, J=2 Hz), 8.07-8.10 (1.3H, m), 8.42-8.45 (1.0H, m), 9.95 (0.7H, brs),10.08 (0.3H, brs)

PREPARATION EXAMPLE 211

A mixture of 0.16 g of3-bromo-N-[4,6-dibromo-2-(N,N′-dimethylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide,0.12 ml of N,N-dimethylcarbamoyl chloride and 2 ml of pyridine wasstirred at 80° C. for 5 hours, and then allowed to cool to roomtemperature. Water was poured into the reaction mixture, and the mixturewas extracted with ethyl acetate. The organic layer was washedsuccessively with water and an aqueous saturated sodium chloridesolution, dried over anhydrous magnesium sulfate, and concentrated underreduced pressure. The resulting residue was subjected to silica gelcolumn chromatography to obtain 0.12 g of the present compound (211) ofthe formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.35 (4.5H, s), 2.49 (2.0H, s), 2.57(1.0H, brs), 2.67 (1.5H, brs), 2.73 (1.0H, s), 3.05 (2.0H, s), 7.10(0.7H, s), 7.34 (0.7H, s), 7.39 (0.3H, s), 7.52-7.57 (1.3H, m), 7.97(0.7H, d, J=2 Hz), 8.06 (0.3H, s), 8.11 (1.0H, dd, J=8 Hz, 2 Hz),8.41-8.45 (1.0H, m), 10.49 (0.7H, s), 10.62 (0.3H, s)

PREPARATION EXAMPLE 212

According to the same manner as that of Preparation Example 160,3-bromo-N-[4,6-dibromo-2-(N-methylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamidewas used in place of3-bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideto obtain the present compound (212) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.50 (6H, s), 3.28 (3H, s), 7.38 (1H, dd,J=8 Hz, 5 Hz), 7.46 (1H, d, J=2 Hz), 7.50 (1H, s), 7.55 (1H, d, J=2 Hz),7.78 (1H, s), 7.86 (1H, d, J=8 Hz), 8.46 (1H, d, J=5 Hz), 10.20 (1H, s).

PREPARATION EXAMPLE 213

According to the same manner as that of Preparation Example 114,2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6,8-dibromo-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain the present compound (213) of the formula:

¹H-NMR (DMSO-d₆) δ (ppm): 2.87 (3H, s), 3.46-3.66 (3H, brm), 7.46 (1H,s), 7.58-7.61 (2H, m), 8.13-8.18 (2H, m), 8.47 (1H, dd, J=5 Hz, 2 Hz),10.54 (1H, s), 10.61 (1H, s)

PREPARATION EXAMPLE 214

According to the same manner as that of Preparation Example 34,2-methoxyethyl chloroformate was used in place of methyl chloroformateto obtain the present compound (214) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.21 (3H, s), 3.39 (3H, brs), 3.61 (2H,brs), 4.31 (2H, brs), 6.96 (1H, brs), 7.01 (1H, s), 7.32-7.39 (3H, m),7.85 (1H, dd, J=8 Hz, 2 Hz), 8.03 (1H, brs), 8.41 (1H, d, J=5 Hz), 9.47(1H, s)

PREPARATION EXAMPLE 215

According to the same manner as that of Preparation Example 95, thepresent compound (214) was used in place of the present compound (34) toobtain the present compound (215) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.24 (3H, s), 3.31 (3H, s), 3.58 (2H, t,J=5 Hz), 3.83 (3H, s), 4.32 (2H, brs), 6.98 (1H, s), 7.32-7.37 (2H, m),7.46 (1H, d, J=2 Hz), 7.88 (1H, d, J=8 Hz), 8.34 (1H, d, J=5 Hz), 8.70(1H, s), 9.33 (1H, s)

PREPARATION EXAMPLE 216

According to the same manner as that of Preparation Example 34,2,2,2-trichloroethyl chloroformate was used in place of methylchloroformate to obtain the present compound (216) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.22 (3.0H, s), 4.89 (0.4H, s), 4.97(1.6H, s), 7.41 (1.0H, s), 7.46 (0.8H, s), 7.53 (0.2H, s), 7.62 (1.0H,s), 7.67 (1.0H, dd, J=8 Hz, 5 Hz), 8.24 (1.0H, dd, J=8 Hz, 2 Hz), 8.56(1.0H, dd, J=5 Hz, 2 Hz), 9.52 (0.2H, s), 10.00 (0.8H, s), 10.31-10.36(1.0H, brm), 10.41 (0.8H, s), 10.50 (0.2H, s)

PREPARATION EXAMPLE 217

According to the same manner as that of Preparation Example 195,2,2,2-trichloroethyl chloroformate was used in place of propargylchloroformate to obtain the present compound (217) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 4.83-4.90 (2.0H, brm), 7.40 (1.0H, s),7.60 (1.0H, dd, J=8 Hz, 5 Hz), 7.67 (0.7H, s), 7.74 (0.3H, s), 8.14-8.18(2.0H, m), 8.50 (1.0H, d, J=5 Hz), 9.51 (0.3H, s), 9.99 (0.7H, s), 10.41(0.7H, s), 10.48-10.54 (1.3H, m)

PREPARATION EXAMPLE 218

According to the same manner as that of Preparation Example 34, butylchloroformate was used in place of methyl chloroformate to obtain thepresent compound (218) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 0.90 (3H, brs), 1.36 (2H, brs), 1.56 (2H,brs), 2.15 (3H, s), 3.92-4.06 (2H, brm), 7.34-7.39 (2H, brm), 7.55 (1H,d, J=2 Hz), 7.61 (1H, dd, J=8 Hz, 5 Hz), 8.17 (1H, dd, J=8 Hz, 2 Hz),8.49 (1H, dd, J=5 Hz, 2 Hz), 9.26 (1H, s), 10.13 (1H, s), 10.23 (1H, s)

PREPARATION EXAMPLE 219

According to the same manner as that of Preparation Example 95, thepresent compound (218) was used in place of the present compound (34) toobtain the present compound (219) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 0.93 (3H, t, J=7 Hz), 1.38 (2H, qt, J=7 Hz,7 Hz), 1.65 (2H, tt, J=7 Hz, 7 Hz), 2.23 (3H, s), 3.81 (3H, s), 4.24(2H, t, J=7 Hz), 6.97 (1H, s), 7.34-7.38 (2H, m), 7.44 (1H, d, J=2 Hz),7.88 (1H, dd, J=8 Hz, 2 Hz), 8.35 (1H, s), 8.38 (1H, dd, J=5 Hz, 2 Hz),9.24 (1H, s)

PREPARATION EXAMPLE 220

A mixture of 0.30 g of3-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide,0.10 g of methoxyacetyl chloride and 3 ml of pyridine was stirred atroom temperature for 2.5 hours. Water was poured into the reactionmixture, and the mixture was extracted with ethyl acetate three times.The organic layers were combined, and was washed with an aqueoussaturated sodium chloride solution, dried over anhydrous magnesiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel column chromatography to obtain 0.21 g ofthe present compound (220) of the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.21 (3H, s), 3.50 (3H, s), 4.08 (2H, s),7.02 (1H, s), 7.34-7.40 (3H, m), 7.86 (1H, dd, J=8 Hz, 2 Hz), 8.44 (1H,dd, J=5 Hz, 2 Hz), 8.57 (1H, d, J=5 Hz), 8.85 (1H, d, J=5 Hz), 9.58 (1H,s).

PREPARATION EXAMPLE 221

According to the same manner as that of Preparation Example 34,2-fluoroethyl chloroformate was used in place of methyl chloroformate toobtain the present compound (221) of the formula:

¹H-NMR (DMSO-d₆, TMS) (ppm): 2.13 (3H, s), 4.20-4.34 (2H, m), 4.53-4.70(2H, m), 7.35 (1H, s), 7.39 (1H, s), 7.55 (1H, s), 7.61 (1H, dd, J=8 Hz,5 Hz), 8.17 (1H, dd, J=8 Hz, 2 Hz), 8.50 (1H, dd, J=5 Hz, 2 Hz), 9.49(1H, s), 10.19 (1H, brs), 10.24 (1H, brs)

PREPARATION EXAMPLE 222

According to the same manner as that of Preparation Example 122,6,8-dibromo-2-[1-(3-chloro-2-pyridinyl)-5-thiocyanato-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-onewas used in place of6,8-dibromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-oneto obtain the present compound (222) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.61 (3H, s), 7.10 (1H, d, J=4 Hz), 7.38(1H, d, J=4 Hz), 7.59 (1H, dd, J=8 Hz, 5 Hz), 7.64 (1H, brs), 8.11 (1H,d, J=2 Hz), 8.15 (1H, dd, J=8 Hz, 1Hz), 8.54 (1H, dd, J=5 Hz, 1Hz), 9.35(1H, brs), 10.14 (2H, brs)

PREPARATION EXAMPLE 223

According to the same manner as that of Preparation Example 93,4-bromo-N-[4,6-dibromo-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideand propargyl chloroformate were used in place of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideand methyl chloroformate respectively to obtain the present compound(223) of the formula:

¹H-NMR (DMSO-d₆, TMS) (ppm): 3.55 (1H, s), 4.70 (2H, s), 7.30 (1H, s),7.44 (1H, d, J=1 Hz), 7.49 (1H, dd, J=8 Hz, 5 Hz), 7.64 (1H, s), 8.05(1H, d, J=8 Hz), 8.11 (1H, s), 8.43 (1H, dd, J=5 Hz, 1Hz), 9.60 (1H,brs), 9.94 (1H, brs), 10.22 (1H, brs)

PREPARATION EXAMPLE 224

According to the same manner as that of Preparation Example 93,N-[4,6-dibromo-2-(hydrazinocarbonyl)phenyl]-4,5-dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideand propargyl chloroformate were used in place of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideand methyl chloroformate respectively to obtain the present compound(224) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.55 (1H, s), 4.71 (2H, s), 7.44 (1H, s),7.56-7.64 (2H, m), 8.10 (1H, s), 8.15 (1H, dd, J=8 Hz, 1Hz), 8.51 (1H,dd, J=5 Hz, 1Hz), 9.58 (1H, brs), 10.02 (1H, brs), 10.23 (1H, brs)

PREPARATION EXAMPLE 225

A mixture of 0.10 g of6,8-dibromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-imidazol-2-yl]-4H-3,1-benzoxazine-4-one,0.16 g of methyl carbazate and 10 ml of N,N-dimethylformamide wasstirred at room temperature for 1 day. The reaction mixture was pouredinto water, and extracted with ethyl acetate three times. The organiclayers were combined, washed successively with water and an aqueoussaturated sodium chloride solution, dried over anhydrous sodium sulfate,and concentrated under reduced pressure. The resulting residue wassubjected to silica gel column chromatography to obtain 0.080 g of thepresent compound (125) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.63 (3H, s), 7.59 (1H, dd, J=8 Hz, 5Hz), 7.90 (1H, s), 8.04 (1H, d, J=2 Hz), 8.11 (1H, d, J=8 Hz), 8.24 (1H,s), 8.49 (1H, d, J=5 Hz), 9.36 (1H, brs), 10.17 (1H, brs), 10.27 (1H,brs)

PREPARATION EXAMPLE 226

According to the same manner as that of Preparation Example 122,6,8-dibromo-2-[1-(3-chloro-2-pyridinyl)-5-methylsulfonyl-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-onewas used in place of6,8-dibromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-oneto obtain the present compound (226) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.27 (3H, s), 3.61 (3H, s), 7.11 (1H, d,J=4 Hz), 7.36 (1H, d, J=4 Hz), 7.53 (1H, dd, J=8 Hz, 5 Hz), 7.65 (1H,brs), 8.04 (1H, dd, J=8 Hz, 2 Hz), 8.12 (1H, d, J=2 Hz), 8.46 (1H, dd,J=5 Hz, 2 Hz), 9.36 (1H, brs), 10.16 (1H, brs), 10.22 (1H, brs)

PREPARATION EXAMPLE 227

According to the same manner as that of Preparation Example 122,6,8-dibromo-2-[1-(3-chloro-2-pyridinyl)-5-methylthio-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-onewas used in place of6,8-dibromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-oneto obtain the present compound (227) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.25 (3H, s), 3.60 (3H, s), 6.52 (1H, d,J=4 Hz), 7.27 (1H, d, J=4 Hz), 7.49 (1H, dd, J=8 Hz, 5 Hz), 7.62 (1H,brs), 8.04 (1H, dd, J=8 Hz, 1Hz), 8.07 (1H, d, J=2 Hz), 8.45 (1H, dd,J=5 Hz, 1Hz), 9.34 (1H, brs), 9.77 (1H, brs), 10.10 (1H, brs)

PREPARATION EXAMPLE 228

According to the same manner as that of Preparation Example 72,6-chloro-2-{1-(3-chloro-2-pyridinyl)-3-[1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy]-1H-pyrazol-5-yl}-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (228) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.16 (3H, s), 3.62 (3H, brs), 7.20 (1H,s), 7.37 (1H, dt, J=51 Hz, 4 Hz), 7.38 (1H, s), 7.55 (1H, s), 7.61 (1H,dd, J=8 Hz, 5 Hz), 8.17 (1H, d, J=8 Hz), 8.50 (1H, d, J=5 Hz), 9.32 (1H,s), 10.16 (1H, s), 10.30 (1H, s)

PREPARATION EXAMPLE 229

According to the same manner as that of Preparation Example 114,6-chloro-2-{1-(3-chloro-2-pyridinyl)-3-[1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy]-1H-pyrazol-5-yl}-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain the present compound (229) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.22 (3H, s), 2.91 (3H, s), 3.47-3.68(3H, brm), 7.24 (1H, s), 7.31 (1H, s), 7.37 (1H, dt, J=51 Hz, 4 Hz),7.57 (1H, d, J=2 Hz), 7.61 (1H, dd, J=8 Hz, 5 Hz), 8.17 (1H, dd, J=8 Hz,1Hz), 8.48 (1H, dd, J=5 Hz, 1Hz), 10.32 (1H, s), 10.53 (1H, s)

PREPARATION EXAMPLE 230

According to the same manner as that of Preparation Example 72,6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-(trifluoromethylthio)-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneto obtain the present compound (230) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.15 (3H, s), 3.62 (3H, brs), 7.39 (1H,brs), 7.55 (1H, s), 7.62-7.68 (2H, m), 8.20 (1H, dd, J=8 Hz, 2 Hz), 8.52(1H, dd, J=5 Hz, 2 Hz), 9.32 (1H, brs), 10.16 (1H, brs), 10.36 (1H, brs)

PREPARATION EXAMPLE 231

A mixture of 0.50 g of3-bromo-N-[4,6-dichloro-2-(N,N′-dimethylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide,0.18 g of methyl chloroformate, 0.16 g of pyridine and 10 ml ofacetonitrile were mixed under ice-cooling, and the mixture was stirredfor 3.5 hours under ice-cooling. Water was poured into the reactionmixture, and the mixture was extracted with ethyl acetate. The organiclayer was washed successively with water and an aqueous saturated sodiumchloride solution, dried over anhydrous magnesium sulfate, andconcentrated under reduced pressure. The resulting residue was washedwith a mixture of methyl tert-butyl ether and hexane to obtain 0.47 g ofthe present compound (231) of the formula:

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.73 (1.4H, s), 2.83 (1.6H, s), 2.95(1.6H, s), 3.07 (1.4H, s), 3.49-3.68 (3.0H, m), 7.32-7.44 (2.0H, m),7.62 (1.0H, dd, J=8 Hz, 5 Hz), 7.85 (0.5H, d, J=2 Hz), 7.92 (0.5H, s),8.19 (1.0H, dd, J=8 Hz, 1Hz), 8.49-8.52 (1.0H, m), 10.53 (0.5H, s),10.71 (0.5H, s)

Then, examples of preparation methods for intermediate compounds used inPreparation Examples will be shown in Reference Preparation Examples.

REFERENCE PREPARATION EXAMPLE 1

A mixture of 0.44 g of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one,0.05 g of hydrazine monohydrate and 10 ml of tetrahydrofuran was stirredat room temperature for 2 hours. After the reaction mixture was mixedwith water and ethyl acetate, layers were separated. The organic layerwas washed with water, dried over sodium sulfate, and concentrated underreduced pressure. The resulting residue was subjected to silica gelcolumn chromatography to obtain 0.10 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.16 (3H, s), 4.36 (2H, s), 7.32 (1H, s),7.48 (1H, s), 7.66 (1H, dd, J=4 Hz, 8 Hz), 7.74 (1H, s), 8.22 (1H, d,J=8 Hz), 8.54 (1H, d, J=4 Hz), 9.56 (1H, brs), 10.39 (1H, brs).

REFERENCE PREPARATION EXAMPLE 2

A mixture of 0.44 g of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one,0.05 g of methylhydrazine and 10 ml of tetrahydrofuran was stirred atroom temperature for 2 hours. After the reaction mixture was mixed withwater and ethyl acetate, layers were separated. The organic layer waswashed with water, dried over sodium sulfate, and concentrated underreduced pressure. The resulting residue was subjected to silica gelcolumn chromatography to obtain 0.40 g ofN-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.17 (1.8H, s), 2.30 (1.2H, s), 2.76(1.2H, s), 3.05 (1.8H, s), 4.54 (1.2H, brs), 4.99 (0.8H, brs), 7.16-7.23(1H, m), 7.36 (0.6H, s), 7.46 (0.4H, s), 7.66-7.70 (2H, m), 8.24 (1H, d,J=8 Hz), 8.54 (1H, d, J=4 Hz), 10.25 (0.6H, brs), 10.51 (0.4H, brs).

REFERENCE PREPARATION EXAMPLE 3

A mixture of 0.40 g of2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one,0.09 ml of hydrazine monohydrate and 20 ml of tetrahydrofuran wasstirred at room temperature for 3 hours. Water was poured into thereaction mixture, and the mixture was extracted with ethyl acetate threetimes. The organic layers were combined, washed with an aqueoussaturated sodium chloride solution, dried over anhydrous magnesiumsulfate, and concentrated under reduced pressure to obtain 0.26 g of1-(3-chloro-2-pyridinyl)-N-[2-(hydrazinocarbonyl)-6-methylphenyl]-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

1-(3-Chloro-2-pyridinyl)-N-[2-(hydrazinocarbonyl)-6-methylphenyl]-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.22 (3H, s), 4.05 (2H, s), 7.18-7.40 (5H,m), 7.42 (1H, dd, J=8 Hz, 4 Hz), 7.89 (1H, dd, J=8 Hz, 1Hz), 8.48 (1H,dd, J=4 Hz, 1Hz), 10.04 (1H, s).

REFERENCE PREPARATION EXAMPLE 4

A mixture of 0.27 g of8-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-4H-3,1-benzoxazine-4-one,0.025 ml of hydrazine monohydrate and 10 ml of tetrahydrofuran wasstirred at room temperature for 3 hours. Water was poured into thereaction mixture, and the mixture was extracted with ethyl acetate threetimes. The organic layers were combined, washed with an aqueoussaturated sodium chloride solution, dried over anhydrous magnesiumsulfate, and concentrated under reduced pressure. The resulting residuewas washed with a mixed solvent of chloroform and methyl t-butyl etherto obtain 0.21 g ofN-[2-chloro-6-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[2-chloro-6-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆) δ (ppm): 4.35 (2H, brs), 7.38-7.39 (2H, m), 7.61-7.66(2H, m), 7.79 (1H, s), 8.20 (1H, d, J=8 Hz), 8.53 (1H, d, J=4 Hz), 9.52(1H, s), 10.04 (1H, s).

REFERENCE PREPARATION EXAMPLE 5

A mixture of 0.40 g of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one,0.08 ml of hydrazine monohydrate and 10 ml of tetrahydrofuran wasstirred at room temperature for 3 hours. The reaction mixture was pouredinto water and then filtered. The resulting filter cake was washed withwater and methyl tert-butyl ether. The filter cake was dissolved inethyl acetate, dried over anhydrous magnesium sulfate, and concentratedunder reduced pressure to obtain 0.35 g of3-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideof the formula:

3-Bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆) δ (ppm): 2.14 (3H, s), 4.37 (2H, brs), 7.31 (1H, s),7.38 (1H, s), 7.47 (1H, s), 7.61 (1H, dd, J=8 Hz, 4 Hz), 8.17 (1H, dd,J=8 Hz, 1Hz), 8.50 (1H, dd, J=4 Hz, 1Hz), 9.55 (1H, brs), 10.26 (1H,brs).

REFERENCE PREPARATION EXAMPLE 6

A mixture of 0.88 g of6-chloro-2-[1-(2-chlorophenyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one,0.19 ml of hydrazine monohydrate and 3 ml of tetrahydrofuran was stirredat room temperature for 2 hours. Water was poured into the reactionmixture, and the mixture was extracted with ethyl acetate three times.The organic layers were combined, washed with an aqueous saturatedsodium chloride solution, dried over anhydrous magnesium sulfate, andconcentrated under reduced pressure to obtain 0.94 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-chlorophenyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-chlorophenyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.18 (3H, s), 4.03 (2H, brs), 7.19-7.54(8H, m), 9.74 (1H, s).

REFERENCE PREPARATION EXAMPLE 7

A mixture of 0.50 g of6-chloro-2-[1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one,0.13 ml of hydrazine monohydrate and 20 ml of tetrahydrofuran wasstirred at room temperature for 4 hours. Water was poured into thereaction mixture, and the mixture was extracted with ethyl acetate twotimes. The organic layers were combined, washed with an aqueoussaturated sodium chloride solution, dried over anhydrous magnesiumsulfate, and concentrated under reduced pressure. The resulting residuewas washed with a mixed solvent of ethyl acetate and hexane to obtain0.44 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideof the formula:

N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.19 (3H, s), 4.03 (2H, brs), 7.05 (1H, d,J=2 Hz), 7.19 (1H, d, J=2 Hz), 7.36 (1H, dd, J=8 Hz, 4 Hz), 7.50 (1H,s), 7.83-7.86 (2H, m), 8.46 (1H, dd, J=4 Hz, 1Hz), 9.64 (1H, s).

REFERENCE PREPARATION EXAMPLE 8

To a solution of 3.1 g of1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carbonylchloride in 100 ml of acetonitrile, 1.9 g of2-amino-5-chloro-3-methylbenzoic acid was added. The mixture was stirredat room temperature for 10 minutes and then, 1.0 g of triethylamine wasadded thereto. The mixture was stirred at room temperature for 20minutes and then, 2.0 g of triethylamine was further added thereto.After the mixture was stirred at room temperature for 20 minutes, 1.2 gof methanesulfonyl chloride was added and the mixture was stirred atroom temperature for 3 hours. After the reaction mixture wasconcentrated under reduced pressure, ethyl acetate and water were pouredinto the residue to separate layers. The organic layer was washed withwater, dried over sodium sulfate, and concentrated under reducedpressured. The resulting residue was subjected to silica gel columnchromatography to obtain 4.2 g of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.73 (3H, s), 7.80 (1H, s), 7.82 (1H, dd,J=4 Hz, 8 Hz), 7.90 (1H, s), 7.91 (1H, s), 8.39 (1H, d, J=8 Hz), 8.66(1H, d, J=4 Hz).

REFERENCE PREPARATION EXAMPLE 9

To a solution of 2.0 g of1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carbonylchloride in 50 ml of acetonitrile, 0.98 g of 2-amino-3-methylbenzoicacid was added. The mixture was stirred at room temperature for 10minutes and then, 0.9 ml of triethylamine was added thereto. The mixturewas stirred at room temperature for 20 minutes and then, 1.8 ml oftriethylamine was further added thereto. After the mixture was stirredat room temperature for 20 minutes, 0.56 ml of methanesulfonyl chloridewas added and the mixture was stirred at room temperature for 3 hours.Water was poured into the reaction mixture, and the mixture wasextracted with ethyl acetate two times. The organic layers werecombined, washed with an aqueous saturated sodium chloride solution,dried over anhydrous magnesium sulfate, and concentrated under reducedpressure. The resulting residue was subjected to silica gel columnchromatography to obtain 1.17 g of2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[1-(3-Chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.84 (3H, s), 7.39 (1H, t, J=8 Hz),7.50-7.55 (3H, m), 7.99 (1H, dd, J=8 Hz, 1Hz), 8.01 (1H, d, J=8 Hz),8.59 (1H, dd, J=4.5 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 10

To a solution of 0.80 g of1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carbonylchloride in 20 ml of acetonitrile, 0.44 g of 2-amino-3-chlorobenzoicacid was added. The mixture was stirred at room temperature for 10minutes and then, 0.36 ml of triethylamine was added thereto. Themixture was stirred at room temperature for 20 minutes and then, 0.72 mlof triethylamine was further added thereto. After the mixture wasstirred at room temperature for 20 minutes, 0.22 ml of methanesulfonylchloride was added and the mixture was stirred at room temperature for20 hours. Water was poured into the reaction mixture, and the mixturewas extracted with ethyl acetate two times. The organic layers werecombined, washed with an aqueous saturated sodium chloride solution,dried over anhydrous magnesium sulfate, and concentrated under reducedpressure. The resulting residue was subjected to silica gel columnchromatography to obtain 1.17 g of8-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-4H-3,1-benzoxazine-4-oneof the formula:

8-Chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.43 (1H, t, J=8 Hz), 7.52 (1H, dd, J=8 Hz,4 Hz), 7.53 (1H, s), 7.75 (1H, dd, J=8 Hz, 1Hz), 8.00 (1H, dd, J=8 Hz,1Hz), 8.11 (1H, dd, J=8 Hz, 1Hz), 8.57 (1H, dd, J=4 Hz, 1Hz)

REFERENCE PREPARATION EXAMPLE 11

To a mixture of 0.44 g of3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid, 6 ml ofacetonitrile and 0.20 g of triethylamine was added 0.125 ml ofmethanesulfonyl chloride. After the resulting mixture was stirred atroom temperature for 15 minutes, 0.27 g of2-amino-5-chloro-3-methylbenzoic acid was added and the mixture wasstirred at room temperature for 20 minutes. To the mixture, 0.40 ml oftriethylamine was added. After the mixture was stirred at roomtemperature for 20 minutes, 0.13 ml of methanesulfonyl chloride wasadded and the mixture was stirred at room temperature for 16 hours. Thereaction mixture was filtered and the filter cake was washed with methyltert-butyl ether. The resulting filter cake was dissolved in ethylacetate, washed successively with water and an aqueous saturated sodiumchloride solution, dried over anhydrous magnesium sulfate, andconcentrated under reduced pressure to obtain 0.098 g of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one.In addition, the filtrate was concentrated under reduced pressure, andthe resulting residue was subjected to silica gel column chromatographyto obtain 0.093 g of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.81 (3H, s), 7.25 (1H, s), 7.48-7.51 (2H,m), 7.95-7.98 (2H, m), 8.56 (1H, dd, J=4 Hz, 1Hz)

REFERENCE PREPARATION EXAMPLE 12

To a mixture of 1.0 g of1-(2-chlorophenyl)-3-trifluoromethyl-1H-pyrazole-5-carbonyl chloride and10 ml of acetonitrile was added 0.60 g of2-amino-5-chloro-3-methylbenzoic acid, and the resulting mixture wasstirred at room temperature for 10 minutes. To the mixture, 0.46 ml oftriethylamine was added. After the mixture was stirred at roomtemperature for 20 minutes, 0.92 ml of triethylamine was further addedthereto. After the mixture was stirred at room temperature for 20minutes, 0.28 ml of methanesulfonyl chloride was added thereto and themixture was stirred at room temperature for 3 hours. The reactionmixture was filtered, and the resulting filtrate was concentrated underreduced pressure. The resulting residue was subjected to silica gelcolumn chromatography to obtain 0.98 g of6-chloro-2-[1-(2-chlorophenyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-chloro-2-[1-(2-chlorophenyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.82 (3H, s), 7.45-7.60 (6H, m), 7.99 (1H,s).

REFERENCE PREPARATION EXAMPLE 13

A mixture of 1.22 g of 1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylicacid and 1.15 ml of thionyl chloride was heated to reflux for 2 hours.The reaction mixture was allowed to cool to room temperature and thenconcentrated under reduced pressure. The resulting residue was dissolvedin 15 ml of acetonitrile, and 0.27 g of 2-amino-5-chloro-3-methylbenzoicacid was added thereto. The mixture was stirred at room temperature for10 minutes. To the mixture was added 0.73 ml of triethylamine, and themixture was stirred at room temperature for 20 minutes. Thereto 1.45 mlof triethylamine was further added, and the mixture was stirred at roomtemperature for 20 minutes. Then 0.44 ml of methanesulfonyl chloride wasadded, and the mixture was stirred at room temperature for 3 hours.Water was poured into the reaction mixture, and the mixture wasextracted with ethyl acetate two times. The organic layers werecombined, washed with an aqueous saturated sodium chloride solution,dried over anhydrous magnesium sulfate, and concentrated under reducedpressure. The resulting residue was washed with methyl tert-butyl etherto obtain 0.68 g of6-chloro-2-[1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.82 (3H, s), 7.28 (1H, d, J=2 Hz),7.46-7.49 (2H, m), 7.91 (1H, d, J=2 Hz), 7.95-7.99 (2H, m), 8.57 (1H,dd, J=4 Hz, 1 Hz).

REFERENCE PREPARATION EXAMPLE 14

A mixture of 15.30 g of 3-trifluoromethyl-1H-pyrazole, 16.64 g of2,3-dichloropyridine, 26.42 g of potassium carbonate and 100 ml ofN,N-dimethylformamide was stirred at 130° C. for 14 hours. The reactionmixture was allowed to cool to room temperature and then water waspoured thereto. The mixture was extracted with ethyl acetate two times.The organic layers were combined, washed successively with water and anaqueous saturated sodium chloride solution, dried over magnesiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel column chromatography to obtain 22.88 g of3-chloro-2-(3-trifluoromethyl-1H-pyrazol-1-yl)pyridine of the formula:

3-Chloro-2-(3-trifluoromethyl-1H-pyrazol-1-yl)pyridine

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.75 (1H, d, J=2 Hz), 7.37 (1H, dd, J=8 Hz,4 Hz), 7.95 (1H, dd, J=8 Hz, 1Hz), 8.14 (1H, d, J=1Hz), 8.49 (1H, dd,J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 15

To a mixture of 15 g of3-chloro-2-(3-trifluoromethyl-1H-pyrazol-1-yl)pyridine and 150 ml oftetrahydrofuran was added dropwise 39 ml of a 2.0 mol/L lithiumdiisopropylamide solution in heptane/tetrahydrofuran/ethylbenzene at−78° C., and then stirred at −78° C. for 15 minutes. Carbon dioxide wasintroduced into the mixture at such a rate that the inner temperaturewas retained at −60° C. or lower. After the mixture turned yellow, itwas further stirred at −78° C. for 10 minutes. After the temperature ofthe reaction mixture was allowed to rise to room temperature, 200 ml ofwater and 200 ml of hexane were poured. The aqueous layer was adjustedto pH 10-12 by an addition of a 2N aqueous sodium hydroxide solution andthen layers were separated. The organic layer was extracted with a 0.5Naqueous sodium hydroxide solution. The aqueous layers were combined,washed with diethyl ether, adjusted to around pH 3 by an addition of 2Nhydrochloric acid, and then extracted with methyl tert-butyl ether threetimes. The organic layers were combined, washed with an aqueoussaturated sodium chloride solution, dried over magnesium sulfate, andconcentrated under reduced pressure to obtain 16.08 g of1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxylic acidof the formula:

1-(3-Chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxylic Acid

¹H-NMR (DMSO-d₆) δ (ppm): 7.60 (1H, s), 7.74 (1H, dd, J=8 Hz, 4 Hz),8.30 (1H, dd, J=8 Hz, 1Hz), 8.60 (1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 16

A mixture of 16.08 g of1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxylic acidand 12 ml of thionyl chloride was heated to reflux for 2 hours. Thereaction mixture was allowed to cool to room temperature and subjectedto distillation under reduced pressure (125° C./3 mmHg) to obtain 14.2 gof 1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carbonylchloride of the formula:

1-(3-Chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carbonylChloride

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.52 (1H, s), 7.52 (1H, dd, J=8 Hz, 4 Hz),7.97 (1H, dd, J=8 Hz, 1Hz), 8.53 (1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 17

To a mixture of 18 g of 4-ethoxy-1,1,1-trifluoro-3-butene-2-one and 50ml of methanol was added 5.7 ml of methylhydrazine, and the mixture washeated to reflux for 4 hours. The reaction mixture was allowed to coolto room temperature, concentrated under reduced pressure, and subjectedto distillation under reduced pressure (60° C./15 mmHg) to obtain 8.71 gof 1-methyl-3-trifluoromethyl-1H-pyrazole of the formula:

1-Methyl-3-trifluoromethyl-1H-pyrazole

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.97 (3H, s), 6.51 (1H, d, J=2 Hz) 7.40(1H, d, J=2 Hz).

REFERENCE PREPARATION EXAMPLE 18

To a mixture of 8.71 g of 1-methyl-3-trifluoromethyl-1H-pyrazole and 130ml of tetrahydrofuran was added dropwise 32 ml of a 2.0 mol/L lithiumdiisopropylamide solution in heptane/tetrahydrofuran/ethylbenzene at−78° C. The mixture of stirred at −78° C. for 2 hours and then pouredinto a mixture was dry ice and 50 ml of tetrahydrofuran. The mixture wasstirred for 2 hours while allowing it to rise to around roomtemperature. Water and diethyl ether were poured into the reactionmixture. The aqueous layer was adjusted to pH 10-12 by an addition of a2N aqueous sodium hydroxide solution, and then layers were separated.The resulting aqueous layer was washed with diethyl ether two times,adjusted to around pH 3 by an addition of 2N hydrochloric acid, and thenextracted with methyl tert-butyl ether three times. The organic layerswere combined, washed with an aqueous saturated sodium chloridesolution, dried over magnesium sulfate, and concentrated under reducedpressure to obtain 8.19 g of1-methyl-3-trifluoromethyl-1H-pyrazole-5-carboxylic acid of the formula:

1-Methyl-3-trifluoromethyl-1H-pyrazole-5-carboxylic Acid

¹H-NMR (CDCl₃, TMS) δ (ppm): 4.13 (3H, s), 7.22 (1H, s).

REFERENCE PREPARATION EXAMPLE 19

To a mixture of 15 g of pyrazole and 200 ml of toluene was addeddropwise 23.7 ml of dimethylsulfamoyl chloride at room temperature.Then, 40 ml of triethylamine was added to the mixture, and the mixturewas stirred at room temperature for 18 hours. The reaction mixture wasfiltered, and the filtrate was concentrated under reduced pressure. Theresulting residue was subjected to silica gel column chromatography toobtain 17.6 g of N,N-dimethyl-1H-pyrazole-1-sulfonamide of the formula:

N,N-dimethyl-1H-pyrazole-1-sulfonamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.95 (6H, s), 6.40 (1H, dd, J=2 Hz, J=1Hz), 7.75 (1H, d, J=1 Hz), 7.95 (1H, d, J=2 Hz,).

REFERENCE PREPARATION EXAMPLE 20

To a mixture of 17.6 g of N,N-dimethyl-1H-pyrazole-1-sulfonamide and 200ml of tetrahydrofuran was added dropwise 80 ml of a 1.3M solution ofn-butyl lithium in hexane at −78° C., and the resulting mixture wasstirred at −78° C. for 15 minutes. To the mixture, a solution of 35.8 gof 1,2-dibromo-1,1,2,2-tetrachloroethane in 60 ml of tetrahydrofuran wasadded dropwise, and the resulting mixture was stirred at −78° C. for 15minutes. The reaction mixture was returned to room temperature, andstirred for 1 hour. Water was poured into the reaction mixture, and themixture was extracted with ethyl acetate three times. The organic layerswere combined, washed with an aqueous saturated sodium chloridesolution, dried over magnesium sulfate, and concentrated under reducedpressure. The resulting residue was subjected to silica gel columnchromatography to obtain 21.3 g of5-bromo-N,N-dimethyl-1H-pyrazole-1-sulfonamide of the formula:

5-Bromo-N,N-dimethyl-1H-pyrazole-1-sulfonamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.08 (6H, s), 6.43 (1H, m), 7.61 (1H, m).

REFERENCE PREPARATION EXAMPLE 21

A mixture of 21.3 g of 5-bromo-N,N-dimethyl-1H-pyrazole-1-sulfonamideand 30 ml of trifluoroacetic acid was stirred at room temperature for 2hours. After hexane was poured into the reaction mixture, the mixturewas filtered. After methyl tert-butyl ether was added to the resultingfiltrate, the mixture was washed successively with an aqueous saturatedsodium hydrogen carbonate solution, water and an aqueous saturatedsodium chloride solution, dried over magnesium sulfate, and concentratedunder reduced pressure to obtain 10.7 g of 3-bromo-1H-pyrazole of theformula:

3-Bromo-1H-pyrazole

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.37 (1H, d, J=2 Hz), 7.55 (1H, d, J=2 Hz),12.6 (1H, brs).

REFERENCE PREPARATION EXAMPLE 22

A mixture of 10.7 g of 3-bromo-1H-pyrazole, 11.8 g of2,3-dichloropyridine, 57.3 g of cesium carbonate and 80 ml ofN,N-dimethylformamide was stirred at 100° C. for 8 hours. The reactionmixture was allowed to cool to room temperature, and water was pouredthereto. The mixture was extracted with methyl tert-butyl ether twotimes. The organic layers were combined, washed successively with waterand an aqueous saturated sodium chloride solution, dried over magnesiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel column chromatography to obtain 12.9 g of2-(3-bromo-1H-pyrazol-1-yl)-3-chloropyridine of the formula:

2-(3-Bromo-1H-pyrazole-1-yl)-3-chloropyridine

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.51 (1H, d, J=2 Hz), 7.31 (1H, dd, J=8 Hz,4 Hz), 7.91 (1H, dd, J=8 Hz, 1Hz), 8.04 (1H, d, J=2 Hz), 8.45 (1H, dd,J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 23

To a mixture of 9.2 g of 2-(3-bromo-1H-pyrazol-1-yl)-3-chloropyridineand 80 ml of tetrahydrofuran was added dropwise 21.3 ml of a 2.0Mlithium diisopropylamide solution inheptane/tetrahydrofuran/ethylbenzene at −78° C. The resulting mixturewas stirred at −78° C. for 15 minutes, poured to a mixture of dry iceand 50 ml of tetrahydrofuran, and stirred for 1 hour with allowing it torise to around room temperature. After water and diethyl ether werepoured into the reaction mixture, the aqueous layer was adjusted to pH10-12 by an addition of a 2N aqueous sodium hydroxide solution andlayers were separated. The resulting aqueous layer was washed withdiethyl ether two times, adjusted to around pH 3 by an addition of 2Nhydrochloric acid, and extracted with methyl tert-butyl ether threetimes. The organic layers were combined, washed with an aqueoussaturated sodium chloride solution, dried over magnesium sulfate, andconcentrated under reduced pressure to obtain 7.96 g of3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid of theformula:

3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic Acid

¹H-NMR (DMSO-d₆) δ (ppm): 7.25 (1H, s), 7.68 (1H, dd, J=8 Hz, 4 Hz),8.24 (1H, dd, J=8 Hz, J=1 Hz), 8.56 (1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 24

To a mixture of 12.96 g of 4,4,4-trifluoro-1-(2-furyl)-1,3-butanedione,8.56 g of sodium acetate and 40 ml of acetic acid was added 11.26 g of2-chlorophenylhydrazine hydrochloride at room temperature. The mixturewas stirred at 60° C. for 1 hour, and concentrated under reducedpressure. After the reaction mixture was concentrated under reducedpressure and water was poured into the residue, the mixture wasextracted with chloroform three times. The organic layers were combined,washed with an aqueous saturated sodium chloride solution, dried overmagnesium sulfate, and concentrated under reduced pressure. Theresulting residue was subjected to silica gel column chromatography toobtain 18.43 g of1-(2-chlorophenyl)-5-(2-furyl)-3-trifluoromethyl-1H-pyrazole of theformula:

1-(2-Chlorophenyl)-5-(2-furyl)-3-trifluoromethyl-1H-pyrazole

¹H-NMR (CDCl₃, TMS) δ (ppm): 5.76 (1H, d, J=3 Hz), 6.31 (1H, dd, J=3 Hz,2 Hz), 6.95 (1H, s), 7.40 (1H, d, J=2 Hz), 7.43-7.59 (4H, m).

REFERENCE PREPARATION EXAMPLE 25

An aqueous solution of 27.94 g of potassium permanganate in 100 ml ofwater was added dropwise to a mixture of 18.43 g of1-(2-chlorophenyl)-5-(2-furyl)-3-trifluoromethyl-1H-pyrazole and 250 mlof acetone with being kept at 40° C. or lower. Then, the mixture wasstirred at room temperature for 20 hours. The reaction mixture wasfiltered through Celite (registered trademark) to obtain a filtrate. Thefiltrate was adjusted to pH 10-12 by an addition of a 2N aqueous sodiumhydroxide solution, and then extracted with ethyl acetate two times. Theaqueous layer was adjusted to around pH 3 by an addition of 2 Nhydrochloric acid, and then extracted with methyl tert-butyl ether threetimes. The organic layers were combined, washed with an aqueoussaturated sodium chloride solution, dried over magnesium sulfate, andconcentrated under reduced pressure to obtain 10.65 g of1-(2-chlorophenyl)-3-trifluoromethyl-1H-pyrazole-5-carboxylic acid ofthe formula:

1-(2-Chlorophenyl)-3-trifluoromethyl-1H-pyrazole-5-carboxylic Acid

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.33 (1H, s), 7.42-7.54 (4H, m)

REFERENCE PREPARATION EXAMPLE 26

A mixture of 10.65 g of1-(2-chlorophenyl)-3-trifluoromethyl-1H-pyrazole-5-carboxylic acid and 8ml of thionyl chloride heated to reflux for 2 hours. The reactionmixture was allowed to cool to room temperature, concentrated underreduced pressure, and subjected to distillation under reduced pressure(110° C./5 mmHg) to obtain 8.39 g of1-(2-chlorophenyl)-3-trifluoromethyl-1H-pyrazole-5-carbonyl chloride ofthe formula:

1-(2-Chlorophenyl)-3-trifluoromethyl-1H-pyrazole-5-carbonyl Chloride

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.42-7.57 (5H, m).

REFERENCE PREPARATION EXAMPLE 27

A mixture of 2 g of pyrazole, 4.34 g of 2,3-dichloropyridine, 9.58 g ofcesium carbonate and 40 ml N,N-dimethylformamide was stirred at 100° C.for 8 hours. The reaction mixture was allowed to cool to roomtemperature, and water was added thereto. The mixture was extracted withmethyl tert-butyl ether three times. The organic layers were combined,washed successively with water and an aqueous saturated sodium chloridesolution, dried over magnesium sulfate, and concentrated under reducedpressure. The resulting residue was subjected to silica gel columnchromatography to obtain 3.57 g of 3-chloro-2-(1H-pyrazol-1-yl)pyridineof the formula:

3-Chloro-2-(1H-pyrazole-1-yl)pyridine

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.50 (1H, dd, J=2 Hz, 1Hz), 7.28 (1H, dd,J=8 Hz, 4 Hz), 7.83 (1H, d, J=1 Hz), 7.92 (1H, dd, J=8 Hz, 1Hz), 8.17(1H, d, J=2 Hz), 8.46 (1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 28

To a mixture of 2.0 g of 3-chloro-2-(1H-pyrazol-1-yl)pyridine and 100 mlof tetrahydrofuran was added dropwise 6.7 ml of a 2.0 mol/L lithiumdiisopropylamide solution in heptane/tetrahydrofuran/ethylbenzene at−78° C. The mixture was stirred at −78° C. for 10 minutes, poured into amixture of dry ice and 50 ml of tetrahydrofuran, and stirred for 0.5hour with allowing it to rise to around room temperature. After waterand diethyl ether were added to the reaction mixture, the aqueous layerwas adjusted to pH 10-12 by an addition of a 2N aqueous sodium hydroxidesolution and layers were separated. After the aqueous layer was washedwith diethyl ether two times, the aqueous layer was adjusted to aroundpH 3 by an addition of 2N hydrochloric acid, and the mixture wasextracted with methyl tert-butyl ether three times. The organic layerswere combined, washed with an aqueous saturated sodium chloridesolution, dried over magnesium sulfate, and concentrated under reducedpressure to obtain 1.22 g of1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid of the formula:

1-(3-Chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic Acid

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.10 (1H, d, J=2 Hz), 7.42 (1H, dd, J=8 Hz,4 Hz), 7.82 (1H, d, J=2 Hz), 7.91 (1H, dd, J=8 Hz, 1Hz), 8.51 (1H, dd,J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 29

A mixture of 16.3 g of isatoic anhydride, 10.4 g of ethyl carbazate and50 ml of ethanol was heated to reflux for 3 hours. After the reactionmixture was allowed to cool to around room temperature, ethyl acetatewas added thereto and the mixture was washed with water two times. Theorganic layer was dried over anhydrous sodium sulfate and concentratedunder reduced pressure. The resulting residue was washed with methyltert-butyl ether to obtain 14.9 g ofN-(2-aminobenzoyl)-N′-ethoxycarbonylhydrazine of the formula:

N-(2-aminobenzoyl)-N′-ethoxycarbonylhydrazine

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.28 (3H, t, J=8 Hz), 4.22 (2H, q, J=8 Hz),5.45 (2H, brs), 6.63-6.68 (2H, m), 6.85 (1H, brs), 7.22 (1H, brs), 7.43(1H, d, J=8 Hz), 7.95 (1H, brs).

REFERENCE PREPARATION EXAMPLE 30

A mixture of 8.86 g of N-methylisatoic anhydride, 5.73 g of ethylcarbazate and 25 ml of ethanol was heated to reflux for 2 hours. Afterthe reaction mixture was allowed to around room temperature, ethylacetate was added thereto and the mixture was washed with water twotimes. The organic layer was dried over anhydrous sodium sulfate, andconcentrated under reduced pressure. The resulting residue was washedwith methyl tert-butyl ether to obtain 5.99 g ofN-(2-methylaminobenzoyl)-N′-ethoxycarbonylhydrazine of the formula:

N-(2-methylaminobenzoyl)-N′-ethoxycarbonylhydrazine

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.28 (3H, t, J=7 Hz), 2.85 (3H, d, J=5 Hz),4.21 (2H, q, J=7 Hz), 6.55-6.59 (1H, m), 6.66 (1H, d, J=8 Hz), 6.78 (1H,brs), 7.29-7.37 (2H, m), 7.43 (1H, dd, J=8 Hz, 1Hz), 7.91 (1H, brs).

REFERENCE PREPARATION EXAMPLE 31-(1)

A mixture of 1.0 g of1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxylic acidand 2 ml of thionyl chloride was heated to reflux for 2 hours. Thereaction mixture was allowed to cool to room temperature, andconcentrated under reduced pressure. The resulting residue was dissolvedin 15 ml of acetonitrile, and 0.49 g of 2-amino-3,5-dimethylbenzoic acidwas added thereto. The mixture was stirred at room temperature for 30minutes. To the mixture, 0.7 ml of triethylamine was added, and themixture was stirred at room temperature for 30 minutes. Further 1.4 mlof triethylamine was added, and the mixture was stirred at roomtemperature for 30 minutes. Then 0.5 ml of methanesulfonyl chloride wasadded, and the mixture was stirred at room temperature for 5 hours.Water was poured into the reaction mixture, and the mixture wasconcentrated under reduced pressure. The resulting residue was washedwith water and methyl tert-butyl ether to obtain 0.71 g of2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-6,8-dimethyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[1-(3-Chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-yl]-6,8-dimethyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.72 (3H, s), 2.37 (3H, s), 7.54 (1H, s),7.77 (1H, s), 7.78-7.85 (2H, m), 8.39 (1H, d, J=8 Hz), 8.66 (1H, d, J=4Hz).

REFERENCE PREPARATION EXAMPLE 31-(2)

According to the same manner as that of Reference Preparation Example 1,2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-6,8-dimethyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4,6-dimethyl-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[4,6-dimethyl-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.11 (3H, s), 2.27 (3H, s), 4.34 (2H,brs), 7.11 (1H, s), 7.17 (1H, s), 7.66 (1H, dd, J=8 Hz, 4 Hz), 7.74 (1H,s), 8.21 (1H, d, J=8 Hz), 8.53 (1H, d, J=4 Hz), 9.37 (1H, brs), 10.26(1H, brs).

REFERENCE PREPARATION EXAMPLE 32-(1)

According to the same manner as that of Reference Preparation Example31-(1), 2-amino-3-bromo-5-methylbenzoic acid was used in place of2-amino-3,5-dimethylbenzoic acid to obtain8-bromo-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-6-methyl-4H-3,1-benzoxazine-4-oneof the formula:

8-Bromo-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-6-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.41 (3H, s), 7.77 (1H, dd, J=8 Hz, 4Hz), 7.87 (1H, s), 7.93 (1H, s), 7.98 (1H, s), 8.36 (1H, d, J=8 Hz),8.63 (1H, d, J=4 Hz).

REFERENCE PREPARATION EXAMPLE 32-(2)

According to the same manner as that of Reference Preparation Example 1,8-bromo-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-6-methyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[6-bromo-2-(hydrazinocarbonyl)-4-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[6-bromo-2-(hydrazinocarbonyl)-4-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.31 (3H, s), 4.33 (2H, brs), 7.24 (1H,s), 7.43 (1H, s), 7.57-7.65 (2H, m), 8.15 (1H, d, J=8 Hz), 8.49 (1H, d,J=4 Hz), 9.38 (1H, brs), 10.31 (1H, brs).

REFERENCE PREPARATION EXAMPLE 33-(1)

According to the same manner as that of Reference Preparation Example31-(1), 2-amino-6-chlorobenzoic acid was used in place of2-amino-3,5-dimethylbenzoic acid to obtain5-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-4H-3,1-benzoxazine-4-oneof the formula:

5-Chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-yl]-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 6.91 (1H, d, J=8 Hz), 7.68 (1H, d, J=8Hz), 7.77 (1H, t, J=8 Hz), 7.83 (1H, dd, J=8 Hz, 4 Hz), 7.91 (1H, s),8.37 (1H, d, J=8 Hz), 8.64 (1H, d, J=4 Hz).

REFERENCE PREPARATION EXAMPLE 33-(2)

According to the same manner as that of Reference Preparation Example1,5-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[3-chloro-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[3-chloro-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 4.47 (2H, brs), 7.32-7.50 (3H, m),7.65-7.75 (2H, m), 8.25 (1H, d, J=8 Hz), 8.56 (1H, d, J=4 Hz), 9.58 (1H,brs), 10.29 (1H, brs).

REFERENCE PREPARATION EXAMPLE 34-(1)

According to the same manner as that of Reference Preparation Example31-(1), 2-amino-5-chlorobenzoic acid was used in place of2-amino-3,5-dimethylbenzoic acid to obtain6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.02 (1H, d, J=8 Hz), 7.83 (1H, dd, J=8Hz, 4 Hz), 7.87-7.92 (2H, m), 8.08 (1H, s), 8.37 (1H, d, J=8 Hz), 8.64(1H, d, J=4 Hz).

REFERENCE PREPARATION EXAMPLE 34-(2)

According to the same manner as that of Reference Preparation Example 1,6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4-chloro-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[4-chloro-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.52-7.56 (2H, m), 7.73 (1H, dd, J=8 Hz,4 Hz), 7.85 (1H, s), 8.19 (1H, d, J=8 Hz), 8.29 (1H, d, J=8 Hz), 8.58(1H, d, J=4 Hz), 10.30 (1H, brs), 12.52 (1H, brs)

REFERENCE PREPARATION EXAMPLE 35-(1)

According to the same manner as that of Reference Preparation Example31-(1), 2-amino-3,5-dibromobenzoic acid was used in place of2-amino-3,5-dimethylbenzoic acid to obtain2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-6,8-dibromo-4H-3,1-benzoxazine-4-oneof the formula:

2-[1-(3-Chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-6,8-dibromo-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.77 (1H, dd, J=8 Hz, 4 Hz), 7.94 (1H,s), 8.19-8.21 (1H, m), 8.35-8.39 (2H, m), 8.63 (1H, d, J=4 Hz).

REFERENCE PREPARATION EXAMPLE 35-(2)

According to the same manner as that of Reference Preparation Example 1,2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-6,8-dibromo-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4,6-dibromo-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[4,6-dibromo-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 4.40 (2H, brs), 7.61 (1H, s), 7.66 (1H,dd, J=8 Hz, 4 Hz), 7.79 (1H, s), 8.08 (1H, s), 8.21 (1H, d, J=8 Hz),8.54 (1H, d, J=4 Hz), 9.60 (1H, brs), 10.62 (1H, brs).

REFERENCE PREPARATION EXAMPLE 36-(1)

According to the same manner as that of Reference Preparation Example31-(1), 2-amino-3,5-diiodobenzoic acid was used in place of2-amino-3,5-dimethylbenzoic acid to obtain2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-6,8-diiodo-4H-3,1-benzoxazine-4-oneof the formula:

2-[1-(3-Chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-6,8-diiodo-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.74 (1H, dd, J=8 Hz, 4 Hz), 7.89 (1H,s), 8.31-8.35 (2H, m), 8.59-8.63 (2H, m).

REFERENCE PREPARATION EXAMPLE 36-(2)

According to the same manner as that of Reference Preparation Example 1,2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-6,8-diiodo-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4,6-diiodo-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[4,6-diiodo-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 4.39 (2H, brs), 7.66 (1H, dd, J=8 Hz, 4Hz), 7.71 (1H, s), 7.79 (1H, s), 8.20 (1H, d, J=8 Hz), 8.33 (1H, s),8.53 (1H, d, J=4 Hz), 9.51 (1H, brs), 10.58 (1H, brs).

REFERENCE PREPARATION EXAMPLE 37-(1)

According to the same manner as that of Reference Preparation Example31-(1), 2-amino-4-chlorobenzoic acid was used in place of2-amino-3,5-dimethylbenzoic acid to obtain7-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-4H-3,1-benzoxazine-4-oneof the formula:

7-Chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.02 (1H, s), 7.68 (1H, d, J=8 Hz), 7.84(1H, dd, J=8 Hz, 4 Hz), 7.91 (1H, s), 8.10 (1H, d, J=8 Hz), 8.38 (1H, d,J=8 Hz), 8.64 (1H, d, J=4 Hz)

REFERENCE PREPARATION EXAMPLE 37-(2)

According to the same manner as that of Reference Preparation Example 1,7-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[5-chloro-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[5-chloro-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.31 (1H, d, J=8 Hz), 7.55 (1H, s), 7.75(1H, dd, J=8 Hz, 4 Hz), 7.82 (1H, d, J=8 Hz), 8.27 (1H, s), 8.31 (1H, d,J=8 Hz), 8.59 (1H, d, J=4 Hz), 10.32 (1H, brs), 12.86 (1H, brs).

REFERENCE PREPARATION EXAMPLE 38-(1)

According to the same manner as that of Reference Preparation Example31-(1), 2-amino-5-methylbenzoic acid was used in place of2-amino-3,5-dimethylbenzoic acid to obtain2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-6-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[1-(3-Chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-yl]-6-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.43 (3H, s), 6.94 (1H, d, J=8 Hz), 7.69(1H, d, J=8 Hz), 7.80-7.85 (2H, m), 7.92 (1H, s), 8.36 (1H, d, J=8 Hz),8.63 (1H, d, J=4 Hz)

REFERENCE PREPARATION EXAMPLE 38-(2)

According to the same manner as that of Reference Preparation Example 1,2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-6-methyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[2-(hydrazinocarbonyl)-4-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[2-(hydrazinocarbonyl)-4-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.29 (3H, s), 4.71 (2H, brs), 7.29 (1H,d, J=8 Hz), 7.51-7.54 (1H, m), 7.61-7.63 (1H, m), 7.72-7.74 (1H, m),8.07 (1H, d, J=8 Hz), 8.29 (1H, d, J=8 Hz), 8.56-8.59 (1H, m), 10.13(1H, brs), 12.52 (1H, brs)

REFERENCE PREPARATION EXAMPLE 39-(1)

According to the same manner as that of Reference Preparation Example31-(1), 2-amino-6-methylbenzoic acid was used in place of2-amino-3,5-dimethylbenzoic acid to obtain2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-5-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[1-(3-Chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-yl]-5-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.68 (3H, s), 6.82 (1H, d, J=8 Hz) 7.44(1H, d, J=8 Hz), 7.70 (1H, t, J=8 Hz), 7.82 (1H, dd, J=8 Hz, 4 Hz), 7.85(1H, s), 8.36 (1H, d, J=8 Hz), 8.64 (1H, d, J=4 Hz).

REFERENCE PREPARATION EXAMPLE 39-(2)

According to the same manner as that of Reference Preparation Example 1,2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-5-methyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[2-(hydrazinocarbonyl)-3-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[2-(hydrazinocarbonyl)-3-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.27 (3H, s), 4.48 (2H, brs), 7.11 (1H,d, J=8 Hz), 7.24-7.35 (2H, m), 7.65-7.72 (2H, m), 8.25 (1H, d, J=8 Hz),8.55 (1H, d, J=4 Hz), 9.35 (1H, brs), 10.15 (1H, brs)

REFERENCE PREPARATION EXAMPLE 40-(1)

According to the same manner as that of Reference Preparation Example31-(1), 2-amino-3,5-dichlorobenzoic acid was used in place of2-amino-3,5-dimethylbenozoic acid to obtain2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-6,8-dichloro-4H-3,1-benzooxazine-4-oneof the formula:

2-[1-(3-Chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-yl]-6,8-dichloro-4H-3,1-benzooxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.78 (1H, dd, J=8 Hz, 4 Hz), 7.95 (1H,s), 8.06 (1H, s), 8.14 (1H, s), 8.37 (1H, d, J=8 Hz), 8.63 (1H, d, J=4Hz).

REFERENCE PREPARATION EXAMPLE 40-(2)

According to the same manner as that of Reference Preparation Example 1,2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-6,8-dichloro-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4,6-dichloro-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[4,6-dichloro-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 4.38 (2H, brs), 7.47 (1H, s), 7.66 (1H,dd, J=8 Hz, 4 Hz), 7.79 (1H, s), 7.86 (1H, s), 8.21 (1H, d, J=8 Hz),8.53 (1H, d, J=4 Hz), 9.64 (1H, brs), 10.63 (1H, brs).

REFERENCE PREPARATION EXAMPLE 41-(1)

To a mixture of 1.7 g of 2-amino-5-chlorobenzoic acid and 100 ml ofN,N-dimethylformamide was added 1.8 g of N-bromosuccinimide at roomtemperature, and the mixture was stirred at room temperature for 10hours. Water was poured into the reaction mixture, and a depositedprecipitate was collected by filtration to obtain 1.1 g of2-amino-3-bromo-5-chlorobenzoic acid of the formula:

2-Amino-3-bromo-5-chlorobenzoic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 6.87 (2H, brs), 7.74 (1H, d, J=2 Hz),7.76 (1H, d, J=2 Hz).

REFERENCE PREPARATION EXAMPLE 41-(2)

According to the same manner as that of Reference Preparation Example31-(1), 2-amino-3-bromo-5-chlorobenzoic acid was used in place of2-amino-3,5-dimethylbenzoic acid to obtain8-bromo-6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-4H-3,1-benzoxazine-4-oneof the formula:

8-Bromo-6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.77 (1H, dd, J=8, 5 Hz), 7.94 (1H, s),8.10 (1H, d, J=2 Hz), 8.27 (1H, d, J=2 Hz), 8.37 (1H, d, J=8 Hz), 8.63(1H, d, J=4 Hz).

REFERENCE PREPARATION EXAMPLE 41-(3)

According to the same manner as that of Reference Preparation Example 1,8-bromo-6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4-H-3,1-benzoxazine-4-oneto obtainN-[6-bromo-4-chloro-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[6-bromo-4-chloro-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 4.35 (2H, brs), 7.50 (1H, s), 7.66 (1H,dd, J=8 Hz, 4 Hz), 7.79 (1H, s), 7.98 (1H, s), 8.21 (1H, d, J=8 Hz),8.53 (1H, d, J=4 Hz), 9.60 (1H, brs), 10.63 (1H, brs)

REFERENCE PREPARATION EXAMPLE 42-(1)

According to the same manner as that of Reference Preparation Example31-(1), 2-amino-4-methylbenzoic acid was used in place of2-amino-3,5-dimethylbenzoic acid to obtain2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-7-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[1-(3-Chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-yl]-7-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.41 (3H, s), 6.84 (1H, s), 7.46 (1H, d,J=8 Hz), 7.82-7.85 (2H, m), 8.00 (1H, d, J=8 Hz), 8.37 (1H, d, J=8 Hz),8.64 (1H, d, J=4 Hz).

REFERENCE PREPARATION EXAMPLE 42-(2)

According to the same manner as that of Reference Preparation Example 1,2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-7-methyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[2-(hydrazinocarbonyl)-5-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

REFERENCE PREPARATION EXAMPLE 43-(1)

A mixture of 1.85 g of 2-amino-5-chloro-3-methylbenzoic acid, 0.90 g oftriphosgene and 10 ml of tetrahydrofuran was stirred at room temperaturefor 5 hours. The reaction mixture was concentrated under reducedpressure, and a precipitated crystal was washed with water to obtain1.20 g of 6-chloro-8-methyl-1H-benzo[d]-1,3-oxazine-2,4-dione of theformula:

6-Chloro-8-methyl-1H-benzo[d]-1,3-oxazine-2,4-dione

¹H-NMR (DMSO-d, TMS) δ (ppm): 2.33 (3H, s), 7.69 (1H, d, J=2 Hz), 7.73(1H, d, J=2 Hz), 11.18 (1H, s).

REFERENCE PREPARATION EXAMPLE 43-(2)

A mixture of 1.05 g of6-chloro-8-methyl-1H-benzo[d]-1,3-oxazine-2,4-dione, 0.46 g of methylcarbazate and 20 ml of methanol was heated to reflux for 3 hours. Afterthe reaction mixture was allowed to cool to around room temperature,water was poured thereto and the mixture was extracted with ethylacetate three times. The resulting organic layer was concentrated underreduced pressure, and the residue was washed with toluene to obtain 0.77g of N-(2-amino-5-chloro-3-methylbenzoyl)-N′-methoxycarbonylhydrazine ofthe formula:

N-(2-amino-5-chloro-3-methylbenzoyl)-N′-ethoxycarbonylhydrazine

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.10 (3H, s), 3.63 (3H, s), 6.32 (2H,brs), 7.19 (1H, d, J=2 Hz), 7.45 (1H, d, J=2 Hz), 9.14 (1H, brs), 10.12(1H, brs).

REFERENCE PREPARATION EXAMPLE 44-(1)

To a mixture of 1.9 g of 3-amino-2-naphthoic acid and 100 ml ofN,N-dimethylformamide was added 1.3 g of N-chlorosuccinimde at roomtemperature, and the mixture was stirred at room temperature for 10hours. After water was added to the reaction mixture, a depositedprecipitate was collected by filtration to obtain 1.3 g of3-amino-4-chloro-2-naphthoic acid of the formula:

3-Amino-4-chloro-2-naphthoic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.27-7.31 (1H, m), 7.60-7.64 (1H, m),7.88 (1H, d, J=8 Hz), 7.93 (1H, d, J=8 Hz), 8.53 (1H, s).

REFERENCE PREPARATION EXAMPLE 44-(2)

According to the same manner as that of Reference Preparation Example31-(1), 3-amino-4-chloro-2-naphthoic acid was used in place of2-amino-3,5-dimethylbenzoic acid to obtain10-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-4H-naphtho[2,3-d][1,3]oxazine-4-oneof the formula:

10-Chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-yl]-4H-naphtho[2,3-d][1,3]oxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.77 (1H, t, J=7 Hz), 7.84 (1H, dd, J=8Hz, 4 Hz), 7.87-7.94 (2H, m), 8.24 (1H, d, J=8 Hz), 8.35 (1H, d, J=8Hz), 8.42 (1H, d, J=8 Hz), 8.67 (1H, d, J=4 Hz), 8.91 (1H, s).

REFERENCE PREPARATION EXAMPLE 44-(3)

According to the same manner as that of Reference Preparation Example 1,10-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-4H-naphtho[2,3-d][1,3]oxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[1-chloro-3-(hydrazinocarbonyl)-2-naphthyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[1-chloro-3-(hydrazinocarbonyl)-2-naphthyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 4.39 (2H, brs), 7.65 (1H, dd, J=8 Hz, 4Hz), 7.70 (1H, t, J=8 Hz), 7.78 (1H, t, J=8 Hz), 7.86 (1H, s), 8.05-8.11(2H, m), 8.18-8.24 (2H, m), 8.53 (1H, d, J=4 Hz), 9.70 (1H, brs), 10.77(1H, brs).

REFERENCE PREPARATION EXAMPLE 45-(1)

According to the same manner as that of Reference Preparation Example44-(1), N-bromosuccinimide was used in place of N-chlorosuccinimide toobtain 3-amino-4-bromo-2-naphthoic acid of the formula:

3-Amino-4-bromo-2-naphthoic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.28 (1H, t, J=8 Hz), 7.61 (1H, t, J=8Hz), 7.86 (1H, d, J=8 Hz), 7.92 (1H, d, J=8 Hz), 8.57 (1H, s)

REFERENCE PREPARATION EXAMPLE 45-(2)

According to the same manner as that of Reference Preparation Example31-(1), 3-amino-4-bromo-2-naphthoic acid was used in place of2-amino-3,5-dimethylbenzoic acid to obtain10-bromo-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-4H-naphtho[2,3-d][1,3]oxazine-4-oneof the formula:

10-Bromo-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-4H-naphtho[2,3-d][1,3]oxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.76 (1H, t, J=8 Hz), 7.82 (1H, dd, J=8Hz, 4 Hz), 7.87-7.94 (2H, m), 8.24 (1H, d, J=8 Hz), 8.34 (1H, d, J=8Hz), 8.42 (1H, d, J=8 Hz), 8.67 (1H, d, J=4 Hz), 8.95 (1H, s).

REFERENCE PREPARATION EXAMPLE 45-(3)

According to the same manner as that of Reference Preparation Example 1,10-bromo-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-4H-naphtho[2,3-d][1,3]oxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[1-bromo-3-(hydrazinocarbonyl)-2-naphthyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[1-bromo-3-(hydrazinocarbonyl)-2-naphthyl]-1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 4.37 (2H, brs), 7.64 (1H, dd, J=8 Hz, 4Hz), 7.70 (1H, d, J=8 Hz), 7.77 (1H, t, J=8 Hz), 7.87 (1H, s), 8.05-8.10(2H, m), 8.17-8.24 (2H, m), 8.53 (1H, d, J=4 Hz), 9.66 (1H, brs), 10.80(1H, brs).

REFERENCE PREPARATION EXAMPLE 46-(1)

A mixture of 11.0 g of3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid and 2 mlof thionyl chloride was heated to reflux for 2 hours. The reactionmixture was allowed to cool to room temperature, and concentrated underreduced pressure. The resulting residue was dissolved in 15 ml ofacetonitrile, and 0.88 g of 2-amino-3,5-dibromobenzoic acid was added.The mixture was stirred at room temperature for 30 minutes. To themixture, 0.7 ml of triethylamine was added. After the mixture wasstirred at room temperature for 30 minutes, 1.4 ml of triethylamine wasfurther added. After the mixture was stirred at room temperature for 30minutes, 0.5 ml of methanesulfonyl chloride was added, and the mixturewas stirred at room temperature for 5 hours. Water was poured into thereaction mixture, and the mixture was concentrated under reducedpressure. The resulting residue was washed with water and methyltert-butyl ether to obtain 0.80 g of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6,8-dibromo-4H-3,1-benzoxazine-4-oneof the formula:

2-[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6,8-dibromo-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.56 (1H, s), 7.71 (1H, dd, J=8 Hz, 4Hz), 8.18 (1H, d, J=2 Hz), 8.32 (1H, d, J=8 Hz), 8.35 (1H, d, J=2 Hz),8.59 (1H, d, J=4 Hz).

REFERENCE PREPARATION EXAMPLE 47-(1)

According to the same manner as that of Reference Preparation Example14, 2-chloropyridine was used in place of 2,3-dichloropyridine to obtain2-(3-trifluoromethyl-1H-pyrazol-1-yl)pyridine of the formula:

2-(3-Trifluoromethyl-1H-pyrazol-1-yl)pyridine

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.71 (1H, d, J=2 Hz), 7.27-7.28 (1H, m),7.86 (1H, t, J=8 Hz), 8.04 (1H, d, J=8 Hz), 8.44 (1H, d, J=4 Hz), 8.63(1H, d, J=2 Hz).

REFERENCE PREPARATION EXAMPLE 47-(2)

According to the same manner as that of Reference Preparation Example15, 2-(3-trifluoromethyl-1H-pyrazol-1-yl)pyridine was used in place of3-chloro-2-(3-trifluoromethyl-1H-pyrazol-1-yl)pyridine to obtain1-(2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxylic acid of theformula:

1-(2-Pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxylic Acid

¹H-NMR (DMSO-d₆) δ (ppm): 7.47 (1H, s), 7.59 (1H, dd, J=8 Hz, 5 Hz),7.78 (1H, d, J=8 Hz), 8.09 (1H, t, J=8 Hz), 8.55 (1H, d, J=5 Hz).

REFERENCE PREPARATION EXAMPLE 47-(3)

According to the same manner as that of Reference Preparation Example13, 1-(2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxylic acid wasused in place of 1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acidto obtain6-chloro-2-[1-(2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[1-(2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.15 (3H, s), 7.26 (1H, s), 7.42 (1H, dd,J=8 Hz, 4 Hz), 7.58 (1H, s), 7.79 (1H, d, J=8 Hz), 7.96-8.00 (2H, m),8.43 (1H, d, J=4 Hz).

REFERENCE PREPARATION EXAMPLE 47-(4)

According to the same manner as that of Reference Preparation Example 1,6-chloro-2-[1-(2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-pyridinyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.31 (3H, s), 4.44 (2H, s), 7.34-7.35(2H, m), 7.50-7.55 (2H, m), 7.81 (1H, d, J=8 Hz), 8.07 (1H, t, J=8 Hz),8.48 (1H, d, J=4 Hz), 9.55 (1H, brs), 10.39 (1H, brs).

REFERENCE PREPARATION EXAMPLE 48-(1)

According to the same manner as that of Reference Preparation Example46-(1), 2-amino-3-bromo-5-chlorobenzoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain8-bromo-2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-4H-3,1-benzoxazine-4-oneof the formula:

8-Bromo-2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.56 (1H, s), 7.72 (1H, dd, J=8 Hz, 4Hz), 8.08 (1H, d, J=2 Hz), 8.25 (1H, d, J=2 Hz), 8.32 (1H, dd, J=8 Hz, 2Hz), 8.59 (1H, dd, J=4 Hz, 2 Hz).

REFERENCE PREPARATION EXAMPLE 49-(1)

According to the same manner as that of Reference Preparation Example46-(1), 2-amino-3-bromo-5-methylbenzoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain8-bromo-2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-methyl-4H-3,1-benzoxazine-4-oneof the formula:

8-Bromo-2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-6-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.40 (3H, s), 7.50 (1H, s), 7.71 (1H, dd,J=8 Hz, 4 Hz), 7.91 (1H, s), 7.96 (1H, s), 8.31 (1H, d, J=8 Hz), 8.59(1H, d, J=4 Hz).

REFERENCE PREPARATION EXAMPLE 50

According to the same manner as that of Reference Preparation Example46-(1), 2-amino-3-chlorobenzoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-chloro-4H-3,1-benzoxazine-4-oneof the formula:

2-[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-8-chloro-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.52-7.61 (2H, m), 7.73 (1H, dd, J=8 Hz,4 Hz), 7.93 (1H, dd, J=8 Hz, 2 Hz), 8.04 (1H, dd, J=8 Hz, 2 Hz), 8.32(1H, dd, J=8 Hz, 2 Hz), 8.60 (1H, dd, J=4 Hz, 2 Hz).

REFERENCE PREPARATION EXAMPLE 51-(1)

According to the same manner as that of Reference Preparation Example24, phenylhydrazine was used in place of 2-chlorophenylhydrazine toobtain 5-(2-furyl)-1-phenyl-3-trifluoromethyl-1H-pyrazole of theformula:

5-(2-Furyl)-1-phenyl-3-trifluoromethyl-1H-pyrazole

¹H-NMR (CDCl₃, TMS) δ (ppm): 5.96 (1H, d, J=4 Hz), 6.33 (1H, dd, J=4 Hz,2 Hz), 6.90 (1H, s), 7.43-7.48 (6H, m).

REFERENCE PREPARATION EXAMPLE 51-(2)

According to the same manner as that of Reference Preparation Example25, 5-(2-furyl)-1-phenyl-3-trifluoromethyl-1H-pyrazole was used in placeof 5-(2-furyl)-1-(2-chlorophenyl)-3-trifluoromethyl-1H-pyrazole toobtain 1-phenyl-3-trifluoromethyl-1H-pyrazole-5-carboxylic acid of theformula:

1-Phenyl-3-trifluoromethyl-1H-pyrazole-5-carboxylic Acid

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.29 (1H, s), 7.46-7.51 (5H, m)

REFERENCE PREPARATION EXAMPLE 51-(3)

According to the same manner as that of Reference Preparation Example13, 1-phenyl-3-trifluoromethyl-1H-pyrazole-5-carboxylic acid was used inplace of 1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid toobtain6-chloro-2-(1-phenyl-3-trifluoromethyl-1H-pyrazol-5-yl)-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-(1-phenyl-3-trifluoromethyl-1H-pyrazol-5-yl)-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.88 (3H, s), 7.47-7.54 (7H, m), 7.99 (1H,d, J=2 Hz).

REFERENCE PREPARATION EXAMPLE 51-(4)

According to the same manner as that of Reference Preparation Example 1,6-chloro-2-(1-phenyl-3-trifluoromethyl-1H-pyrazol-5-yl)-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-phenyl-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-phenyl-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.19 (3H, s), 4.41 (2H, brs), 7.32 (1H,d, J=2 Hz), 7.46-7.52 (5H, m), 7.56 (2H, d, J=7 Hz), 9.61 (1H, brs),10.29 (1H, brs).

REFERENCE PREPARATION EXAMPLE 52-(1)

To a mixture of 1.5 g of 2-amino-5-chlorobenzoic acid and 100 ml ofN,N-dimethylformamide was added 1.8 g of N-bromosuccinimide at roomtemperature, and the mixture was stirred at room temperature for 10hours. After 30 ml of water was poured into the reaction mixture, themixture was extracted with ethyl acetate three times. The organic layerswere combined, washed with an aqueous saturated sodium chloridesolution, dried over anhydrous magnesium sulfate, and concentrated underreduced pressure to obtain 1.2 g of 2-amino-5-bromo-3-methylbenzoic acidof the formula:

2-Amino-5-bromo-3-methylbenzoic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.11 (3H, s), 7.33 (1H, d, J=2 Hz), 7.68(1H, d, J=2 Hz).

REFERENCE PREPARATION EXAMPLE 52-(2)

According to the same manner as that of Reference Preparation Example31-(1), 2-amino-5-bromo-3-methylbenzoic acid was used in place of2-amino-3,5-dimethylbenzoic acid to obtain6-bromo-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Bromo-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.733H, s), 7.81 (1H, dd, J=8 Hz, 4 Hz),7.90 (1H, s), 7.93 (1H, s), 8.04 (1H, t, J=1 Hz), 8.39 (1H, d, J=8 Hz),8.66 (1H, d, J=4 Hz).

REFERENCE PREPARATION EXAMPLE 53-(1)

To a mixture of 2.6 g of 2-amino-3-methylbenzoic acid and 100 ml ofN,N-dimethylformamide was added 2.3 g of N-iodosuccinimide at roomtemperature, and the mixture was stirred at room temperature for 10hours. After water was poured to the reaction mixture, a depositedprecipitate was collected by filtration to obtain 1.7 g of2-amino-5-iodo-3-methylbenzoic acid of the formula:

2-Amino-5-iodo-3-methylbenzoic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.08 (3H, s), 7.44 (1H, d, J=1 Hz), 7.86(1H, d, J=1 Hz)

REFERENCE PREPARATION EXAMPLE 53-(2)

According to the same manner as that of Reference Preparation Example31-(1), 2-amino-5-iodo-3-methylbenzoic acid was used in place of2-amino-3,5-dimethylbenzoic acid to obtain2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-6-iodo-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[1-(3-Chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-6-iodo-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.70 (3H, s), 7.81 (1H, dd, J=8 Hz, 4Hz), 7.89 (1H, s), 8.07 (1H, s), 8.19 (1H, s), 8.39 (1H, d, J=8 Hz),8.66 (1H, d, J=4 Hz).

REFERENCE PREPARATION EXAMPLE 54-(1)

A mixture of 1.41 g of ethyl2-(2-chlorobenzoyl)-3-(N,N-dimethylamino)acrylate (a compound describedin JP-A 7-101940), 0.30 g of hydrazine monohydrate and 5 ml of aceticacid was stirred at room temperature for 10 hours. The reaction mixturewas concentrated under reduced pressure. Water was poured into theresidue, and the mixture was extracted with ethyl acetate. The organiclayer was washed with water, dried over anhydrous sodium sulfate, andconcentrated under reduced pressure to obtain ethyl3-(2-chlorophenyl)-1H-pyrazole-4-carboxylate of the formula:

The resulting ethyl 3-(2-chlorophenyl)-1H-pyrazole-4-carboxylate, 1.07 gof methyl iodide, 1.04 g of potassium carbonate and 5 ml ofN,N-dimethylformaide were mixed under ice-cooling, and the mixture wasstirred at room temperature for 10 hours. Water was poured into thereaction mixture, and the mixture was extracted with ethyl acetate. Theorganic layer was washed with water, dried over anhydrous sodiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel column chromatography to obtain 0.72 g ofethyl

3-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxylate of the formula:

and 0.48 g of ethyl5-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxylate.

Ethyl 3-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxylate

¹H-NMR (CDCl₃) δ (ppm): 1.12 (3H, t, J=7 Hz), 3.68 (3H, s), 4.09-4.15(2H, m), 7.31 (1H, dd, J=7 Hz, 2 Hz), 7.38 (1H, td, J=7 Hz, 1Hz), 7.44(1H, td, J=8 Hz, 2 Hz), 7.52 (1H, dd, J=8 Hz, 1Hz), 8.01 (1H, s).

Ethyl 5-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxylate

¹H-NMR (CDCl₃) δ (ppm): 1.13 (3H, t, J=7 Hz), 3.98 (3H, s), 4.14 (2H, q,J=7 Hz), 7.27-7.35 (2H, m), 7.38-7.41 (1H, m), 7.43-7.45 (1H, m), 7.96(1H, s).

REFERENCE PREPARATION EXAMPLE 54-(2)

A mixture of 0.72 g of ethyl3-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxylate, 0.23 g ofpotassium hydroxide, 1 ml of water and 5 ml of ethanol was stirred atroom temperature for 3 days. After the reaction mixture was concentratedunder reduced pressure, water was poured into the resulting residue andthe mixture was washed with methyl tert-butyl ether. The aqueous layerwas adjusted to around pH 3 by an addition of a 10% aqueous citric acid,and then extracted with ethyl acetate. The organic layer was washed withwater, dried over anhydrous sodium sulfate, and concentrated underreduced pressure to obtain 0.61 g of3-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxylic acid of theformula:

3-(2-Chlorophenyl)-1-methyl-1H-pyrazole-4-carboxylic Acid

¹H-NMR (CDCl₃) δ (ppm): 3.66 (3H, s), 7.30 (1H, dd, J=8 Hz, 2 Hz), 7.37(1H, td, J=8 Hz, 1Hz), 7.43 (1H, td, J=8 Hz, 2 Hz), 7.51 (1H, dd, J=8Hz, 1Hz), 8.02 (1H, s).

REFERENCE PREPARATION EXAMPLE 54-(3)

A mixture of 0.61 g of3-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxylic acid, 0.28 ml ofthionyl chloride and 10 ml of toluene was heated to reflux for 1 hour.After the reaction mixture was allowed to cool to room temperature, itwas concentrated under reduced pressure and the resulting residue wasdissolved in 10 ml of acetonitrile. Thereto 0.48 g of2-amino-5-chloro-3-methylbenzoic acid was added, and the resultingmixture was stirred at room temperature for 30 minutes. To the mixture,0.26 g of triethylamine was added, the mixture was stirred at roomtemperature for 30 minutes. Thereto 0.52 g of triethylamine was furtheradded, and the resulting mixture was stirred at room temperature for 30minutes. Then, 0.30 g of methanesulfonyl chloride was added to thereaction mixture under ice-cooling, and the mixture was stirred at roomtemperature for 10 hours. Water and ethyl acetate were poured into thereaction mixture, and 0.26 g of a solid was collected by filtration. Inaddition, the filtrate was separated into two layers. The organic layerwas washed with water, dried over anhydrous sodium sulfate, andconcentrated under reduced pressure. The resulting residue was washedwith ethyl acetate to obtain 0.25 g of a solid. Both of these solidswere6-chloro-2-[3-(2-chlorophenyl)-1-methyl-1H-pyrazol-4-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[3-(2-chlorophenyl)-1-methyl-1H-pyrazol-4-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆) δ (ppm): 1.86 (3H, s), 3.68 (3H, s), 7.52-7.63 (3H, m),7.69-7.72 (2H, m), 7.81 (1H, d, J=2 Hz), 8.18 (1H, s)

REFERENCE PREPARATION EXAMPLE 54-(4)

After 0.19 g of6-chloro-2-[3-(2-chlorophenyl)-1-methyl-1H-pyrazol-4-yl]-8-methyl-4H-3,1-benzoxazine-4-one,0.10 g of hydrazine monohydrate and 10 ml of N-methylpyrrolidinone weremixed under ice-cooling, the mixture was stirred at room temperature for8 hours. Water was poured into the reaction mixture, and the mixture wasextracted with ethyl acetate. The organic layer was washed with water,dried over anhydrous sodium sulfate, and concentrated under reducedpressure to obtain 0.18 g ofN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-3-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxamideof the formula:

N-[4-chloro-2-(hydradinocarbonyl)-6-methylphenyl]-3-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxamide

¹H-NMR (DMSO-d₆) δ (ppm): 2.13 (3H, s), 3.60 (3H, s), 4.39 (2H, brs),7.29 (1H, d, J=2 Hz), 7.42-7.53 (4H, m), 7.60 (1H, d, J=8 Hz), 8.11 (1H,s), 9.53 (2H, brs).

REFERENCE PREPARATION EXAMPLE 55-(1)

According to the same manner as that of Reference Preparation Example54-(2), ethyl 5-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxylate wasused in place of ethyl3-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxylate to obtain5-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxylic acid of theformula:

5-(2-Chlorophenyl)-1-methyl-1H-pyrazole-4-carboxylic Acid

¹H-NMR (CDCl₃) δ (ppm): 3.97 (3H, s), 7.26-7.35 (2H, m), 7.37-7.39 (1H,m), 7.42-7.44 (1H, m), 7.98 (1H, s).

REFERENCE PREPARATION EXAMPLE 55-(2)

According to the same manner as that of Reference Preparation Example54-(3), 5-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxylic acid wasused in place of 3-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxylicacid to obtain6-chloro-2-[5-(2-chlorophenyl)-1-methyl-1H-pyrazol-4-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[5-(2-chlorophenyl)-1-methyl-1H-pyrazol-4-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆) δ (ppm): 1.90 (3H, s), 3.99 (3H, s), 7.40-7.50 (3H, m),7.56 (1H, d, J=8 Hz), 7.71 (1H, d, J=2 Hz), 7.82 (1H, d, J=2 Hz), 8.63(1H, s).

REFERENCE PREPARATION EXAMPLE 55-(3)

According to the same manner as that of Reference Preparation Example54-(4),6-chloro-2-[5-(2-chlorophenyl)-1-methyl-1H-pyrazol-4-yl]-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[3-(2-chlorophenyl)-1-methyl-1H-pyrazol-4-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-5-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxamideof the formula:

N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-5-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxamide

¹H-NMR (DMSO-d₆) δ (ppm): 2.16 (3H, s), 3.94 (3H, s), 4.39 (2H, brs),7.30 (1H, d, J=2 Hz), 7.33-7.46 (5H, m), 8.36 (1H, s), 9.49-9.59 (2H,brm).

REFERENCE PREPARATION EXAMPLE 56-(1)

To a mixture of 1.67 g of 2-amino-3-methoxybenzoic acid and 100 ml ofN,N-dimethylformamide was added 1.3 g of N-chlorosuccinimide at roomtemperature, and the resulting mixture was stirred at room temperaturefor 10 hours. Water was poured into the reaction mixture, and adeposited precipitate was collected by filtration to obtain 1.2 g of2-amino-5-chloro-3-methoxybenzoic acid.

2-Amino-5-chloro-3-methoxybenzoic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.84 (3H, s), 6.99 (1H, s), 7.28 (1H, s).

REFERENCE PREPARATION EXAMPLE 56-(2)

According to the same manner as that of Reference Preparation Example46-(1), 2-amino-5-chloro-3-methoxybenzoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methoxy-4H-3,1-benzoxazine-4-oneof the formula:

2-[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methoxy-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.71 (3H, s), 7.45 (1H, d, J=2 Hz), 7.48(1H, s), 7.57 (1H, d, J=2 Hz), 7.78 (1H, dd, J=8 Hz, 4 Hz), 8.28 (1H,dd, J=8 Hz, 2 Hz), 8.57 (1H, dd, J=4 Hz, 2 Hz).

REFERENCE PREPARATION EXAMPLE 57-(1)

To a mixture of 1.5 g of 2-amino-5-chlorobenzoic acid and 100 ml ofN,N-dimethylformamide was added 2.7 g of N-iodosuccinimide at roomtemperature, and the mixture was stirred at room temperature for 24hours. After 30 ml of water was poured into the reaction mixture, themixture was extracted with ethyl acetate three times. The organic layerswere combined, washed with an aqueous saturated sodium chloridesolution, dried over anhydrous magnesium sulfate, and concentrated underreduced pressure to obtain 1.2 g of 2-amino-5-chloro-3-iodobenzoic acidof the formula:

2-Amino-5-chloro-3-iodobenzoic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 6.76 (2H, brs), 7.75 (1H, d, J=1 Hz),7.87 (1H, d, J=1 Hz).

REFERENCE PREPARATION EXAMPLE 57-(2)

According to the same manner as that of Reference Preparation Example46-(1), 2-amino-5-chloro-3-iodobenzoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-iodo-4H-3,1-benzoxazine-4-oneof the formula:

2-[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-iodo-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.53 (1H, s), 7.69 (1H, dd, J=8 Hz, 4Hz), 8.08 (1H, d, J=2 Hz), 8.29 (1H, d, J=8 Hz), 8.38 (1H, d, J=2 Hz),8.57 (1H, d, J=4 Hz).

REFERENCE PREPARATION EXAMPLE 58

According to the same manner as that of Reference Preparation Example46-(1), 2-amino-3-methoxybenzoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-methoxy-4H-3,1-benzoxazine-4-oneof the formula:

2-[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-methoxy-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 3.67 (3H, s), 7.40 (1H, dd, J=8 Hz, 1Hz),7.46 (1H, s), 7.52 (1H, t, J=8 Hz), 7.61 (1H, dd, J=8 Hz, 1Hz), 7.78(1H, dd, J=8 Hz, 4 Hz), 8.28 (1H, dd, J=8 Hz, 1Hz), 8.57 (1H, dd, J=4Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 59

According to the same manner as that of Reference Preparation Example46-(1), 2-amino-3-trifluoromethylbenzoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-trifluoromethyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-trifluoromethyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.56 (1H, s), 7.69-7.77 (2H, m) 8.15 (1H,d, J=8 Hz), 8.29 (1H, dd, J=8 Hz, 1Hz), 8.37 (1H, d, J=8 Hz), 8.55 (1H,dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 60-(1)

To a solution of 4.8 g of hydrazine monohydrate in 160 ml of ethanol,14.2 g of ethyl trifluoroacetate was added dropwise. The resultingmixture was stirred at room temperature for 1 hour. The reaction mixturewas concentrated under reduced pressure. The resulting residue wasdissolved in 100 ml of ethanol, and 9.9 g of formamidine acetate wasadded thereto. The mixture was stirred for 3 hours under heat refluxing.The reaction mixture was allowed to cool to room temperature, and thenconcentrated under reduced pressure. An aqueous sodium bicarbonatesolution was poured into the resulting residue, and the mixture wasextracted with ethyl acetate two times. The organic layers werecombined, washed successively with water and an aqueous saturated sodiumchloride solution, dried over magnesium sulfate, and concentrated underreduced pressure. The resulting residue was subjected to silica gelcolumn chromatography to obtain 7.0 g of3-trifluoromethyl-1H-1,2,4-triazole of the formula:

3-Trifluoromethyl-1H-1,2,4-triazole

¹H-NMR (CDCl₃, TMS) δ (ppm): 8.48 (1H, s).

REFERENCE PREPARATION EXAMPLE 60-(2)

A mixture of 3.5 g of 3-trifluoromethyl-1H-1,2,4-triazole, 3.8 g of2,3-dichloropyridine, 6.0 g of potassium carbonate and 30 ml ofN,N-dimethylformamide was stirred at 120° C. for 27 hours. After thereaction mixture was allowed to cool to room temperature, water waspoured and the mixture was extracted with ethyl acetate two times. Theorganic layers were combined, washed successively with water and anaqueous saturated sodium chloride solution, dried over magnesiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel column chromatography to obtain 0.72 g of3-chloro-2-(3-trifluoromethyl-1H-1,2,4-triazol-1-yl)pyridine of theformula:

3-Chloro-2-(3-trifluoromethyl-1H-1,2,4-triazol-1-yl)pyridine

¹H-NMR (DMSO-d₆) δ (ppm): 7.47 (1H, dd, J=8 Hz, 5 Hz), 8.01 (1H, dd, J=8Hz, 2 Hz), 8.53 (1H, dd, J=5 Hz, 2 Hz), 8.82 (1H, s).

REFERENCE PREPARATION EXAMPLE 61-(1)

According to the same manner as that of Reference Preparation Example17, ethylhydrazine was used in place of methylhydrazine to obtain1-ethyl-3-trifluoromethyl-1H-pyrazole of the formula:

1-Ethyl-3-trifluoromethyl-1H-pyrazole

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.52 (3H, t, J=7 Hz), 4.23 (2H, q, J=7 Hz),6.51 (1H, d, J=2 Hz), 7.44 (1H, d, J=2 Hz).

REFERENCE PREPARATION EXAMPLE 61-(2)

According to the same manner as that of Reference Preparation Example18, 1-ethyl-3-trifluoromethyl-1H-pyrazole was used in place of1-methyl-3-trifluormethyl-1H-pyrazole to obtain1-ethyl-3-trifluoromethyl-1H-pyrazole-5-carboxylic acid of the formula:

1-Ethyl-3-trifluoromethyl-1H-pyrazole-5-carboxylic Acid

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.51 (3H, t, J=7 Hz), 4.68 (2H, q, J=7 Hz),7.21 (1H, s).

REFERENCE PREPARATION EXAMPLE 61-(3)

According to the same manner as that of Reference Preparation Example13, 1-ethyl-3-trifluoromethyl-1H-pyrazole-5-carboxylic acid was used inplace of 1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid toobtain6-chloro-2-(1-ethyl-3-trifluoromethyl-1H-pyrazol-5-yl)-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-(1-ethyl-3-trifluoromethyl-1H-pyrazol-5-yl)-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.58 (3H, t, J=7 Hz), 2.59 (3H, s), 4.89(2H, q, J=7 Hz), 7.33 (1H, s), 7.69 (1H, d, J=2 Hz), 8.07 (1H, d, J=2Hz).

REFERENCE PREPARATION EXAMPLE 61-(4)

According to the same manner as that of Reference Preparation Example 1,6-chloro-2-(1-ethyl-3-trifluoromethyl-1H-pyrazol-5-yl)-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-ethyl-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-ethyl-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.48 (3H, t, J=7 Hz), 2.30 (3H, s), 4.04(2H, s), 4.66 (2H, q, J=7 Hz), 7.08 (1H, s), 7.29 (1H, s), 7.40 (1H, s),7.45 (1H, brs), 9.81 (1H, brs).

REFERENCE PREPARATION EXAMPLE 62-(1)

A mixture of 2.82 g of ethyl2-(2-chlorobenzoyl)-3-(N,N-dimethylamino)acrylate (a compound describedin JP-A 7-101940), 1.25 g of tert-butylhydrazine hydrochloride and 10 mlof ethanol was heated to reflux for 8 hours. After the reaction mixturewas allowed to cool to room temperature, water was poured and themixture was extracted with ethyl acetate. The organic layer was washedwith water, dried over anhydrous sodium sulfate, and concentrated underreduced pressure. The resulting residue was subjected to silica gelcolumn chromatography to obtain 0.48 g of ethyl1-tert-butyl-5-(2-chlorophenyl)-1H-pyrazole-4-carboxylate of theformula:

Ethyl 1-tert-butyl-5-(2-chlorophenyl)-1H-pyrazole-4-carboxylate

¹H-NMR (CDCl₃) δ (ppm): 1.04 (3H, t, J=7 Hz), 1.47 (9H, s), 3.98-4.12(2H, m), 7.28-7.35 (2H, m), 7.38-7.42 (1H, m), 7.45-7.48 (1H, m), 7.99(1H, s).

REFERENCE PREPARATION EXAMPLE 62-(2)

According to the same manner as that of Reference Preparation Example54-(2), ethyl 1-tert-butyl-5-(2-chlorophenyl)-1H-pyrazole-4-carboxylatewas used in place of ethyl3-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxylate to obtain1-tert-butyl-5-(2-chlorophenyl)-1H-pyrazole-4-carboxylic acid of theformula:

1-tert-Butyl-5-(2-chlorophenyl)-1H-pyrazole-4-carboxylic Acid

¹H-NMR (CDCl₃) δ (ppm): 1.45 (9H, s), 7.25-7.33 (2H, m), 7.39 (1H, td,J=7 Hz, 2 Hz), 7.44 (1H, dd, J=8 Hz, 1Hz), 8.00 (1H, s)

REFERENCE PREPARATION EXAMPLE 62-(3)

According to the same manner as that of Reference Preparation Example54-(3), 1-tert-butyl-5-(2-chlorophenyl)-1H-pyrazole-4-carboxylic acidwas used in place of3-(2-chlorophenyl)-1-methyl-1H-pyrazole-4-carboxylic acid to obtain2-[1-tert-butyl-5-(2-chlorophenyl)-1H-pyrazol-4-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[1-tert-Butyl-5-(2-chlorophenyl)-1H-pyrazole-4-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆) δ (ppm): 1.44 (9H, s), 1.77 (3H, s), 7.47-7.59 (3H, m),7.65-7.68 (2H, m), 7.80 (1H, d, J=2 Hz), 8.18 (1H, s)

REFERENCE PREPARATION EXAMPLE 62-(4)

According to the same manner as that of Reference Preparation Example54-(4),2-[1-tert-butyl-5-(2-chlorophenyl)-1H-pyrazol-4-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[3-(2-chlorophenyl)-1-methyl-1H-pyrazol-4-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtain1-tert-butyl-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-5-(2-chlorophenyl)-1H-pyrazole-4-carboxamideof the formula:

1-tert-Butyl-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-5-(2-chlorophenyl)-1H-pyrazole-4-carboxamide

¹H-NMR (DMSO-d₆) δ (ppm): 1.40 (9H, s), 2.06 (3H, s), 4.37 (2H, brs),7.28 (1H, d, J=2 Hz), 7.38-7.53 (5H, m), 8.10 (1H, s), 9.36 (1H, brs),9.53 (1H, brs).

REFERENCE PREPARATION EXAMPLE 63-(1)

A mixture of 4.62 g of chloral hydrate, 3.5 g of3-chloro-2-methylaniline, 30 g of anhydrous sodium sulfate, 120 ml ofwater and 2 ml of 2N hydrochloric acid was stirred at room temperaturefor 2 hours. Then, to the resulting mixture, 1.8 g of hydroxylaminehydrochloride was added, and the mixture was heated to reflux for 30minutes. The reaction mixture was ice-cooled, and a depositedprecipitate was collected by filtration to obtain 2.5 g ofN-(3-chloro-2-methylphenyl)-2-(hydroxyimino)acetamide of the formula:

N-(3-chloro-2-methylphenyl)-2-(hydroxyimino)acetamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.22 (3H, s), 7.22 (1H, t, J=8 Hz), 7.33(1H, d, J=8 Hz), 7.38 (1H, d, J=8 Hz), 7.67 (1H, s), 9.78 (1H, brs),12.21 (1H, s).

REFERENCE PREPARATION EXAMPLE 63-(2)

To 2.5 g of concentrated sulfuric acid was added 2.5 g ofN-(3-chloro-2-methylphenyl)-2-(hydroxyimino)acetamide at 50° C., and themixture was stirred at 80° C. for 30 minutes. The reaction mixture waspoured into 200 g of ice, and a deposited precipitate was collected byfiltration to obtain 1.3 g of 6-chloro-7-methyl-1H-indole-2,3-dione ofthe formula:

6-Chloro-7-methyl-1H-indole-2,3-dione

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.22 (3H, s), 7.15 (1H, d, J=8 Hz), 7.37(1H, d, J=8 Hz), 11.28 (1H, s).

REFERENCE PREPARATION EXAMPLE 63-(3)

A mixed solution of 1.3 g of 6-chloro-7-methyl-1H-indole-2,3-dione and50 ml of a 2N aqueous sodium hydroxide solution was added dropwise to 2g of aqueous hydrogen peroxide (30%), and the mixture was stirred atroom temperature for 1 hour. The reaction mixture was adjusted to pH 4by an addition of 2N hydrochloric acid, and a deposited precipitate wascollected by filtration to obtain 0.6 g of2-amino-4-chloro-3-methylbenzoic acid of the formula:

2-Amino-4-chloro-3-methylbenzoic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.18 (3H, s), 6.62 (1H, d, J=9 Hz) 7.61(1H, d, J=9 Hz).

REFERENCE PREPARATION EXAMPLE 63-(4)

According to the same manner as that of Reference Preparation Example46-(1), 2-amino-4-chloro-3-methylbenzoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-7-chloro-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[2-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-7-chloro-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.76 (3H, s), 7.55 (1H, s), 7.65 (1H, d,J=9 Hz), 7.77 (1H, dd, J=8 Hz, 4 Hz), 7.94 (1H, d, J=9 Hz), 8.35 (1H,dd, J=8 Hz, 1Hz), 8.64 (1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 64-(1)

According to the same manner as that of Reference Preparation Example14, isopropyl iodide was used in place of 2,3-dichloropyridine to obtain1-isopropyl-3-trifluoromethyl-1H-pyrazole of the formula:

1-Isopropyl-3-trifluoromethyl-1H-pyrazole

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.53 (6H, d, J=7 Hz), 4.53-4.60 (1H, m),6.50 (1H, d, J=2 Hz), 7.45 (1H, d, J=2 Hz).

REFERENCE PREPARATION EXAMPLE 64-(2)

According to the same manner as that of Reference Preparation Example18, 1-isopropyl-3-trifluoromethyl-1H-pyrazole was used in place of1-methyl-3-trifluoromethyl-1H-pyrazole to obtain1-isopropyl-3-trifluoromethyl-1H-pyrazole-5-carboxylic acid of theformula:

1-Isopropyl-3-trifluoromethyl-1H-pyrazole-5-carboxylic Acid

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.53 (6H, d, J=7 Hz), 5.49-5.56 (1H, m),7.17 (1H, s).

REFERENCE PREPARATION EXAMPLE 64-(3)

According to the same manner as that of Reference Preparation Example13, 1-isopropyl-3-trifluoromethyl-1H-pyrazole-5-carboxylic acid was usedin place of 1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid toobtain6-chloro-2-(1-isopropyl-3-trifluoromethyl-1H-pyrazol-5-yl)-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-(1-isopropyl-3-trifluoromethyl-1H-pyrazol-5-yl)-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.62 (6H, d, J=7 Hz), 2.59 (3H, s),5.83-5.90 (1H, m), 7.31 (1H, s), 7.68 (1H, s), 8.07 (1H, s).

REFERENCE PREPARATION EXAMPLE 64-(4)

According to the same manner as that of Reference Preparation Example 1,6-chloro-2-(1-isopropyl-3-trifluoromethyl-1H-pyrazol-5-yl)-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-isopropyl-3-trifluoromethyl-1H-pyrazole-5-carboxamide of the formula:

N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-isopropyl-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.44 (6H, d, J=7 Hz), 2.25 (3H, s), 4.36(2H, s), 5.42-5.47 (1H, m), 7.34 (1H, s), 7.36 (1H, s), 7.50 (1H, s),9.61 (1H, brs), 10.16 (1H, brs)

REFERENCE PREPARATION EXAMPLE 65

According to the same manner as that of Reference Preparation Example46-(1), 2-amino-3,6-dichlorobenzoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-5,8-dichloro-4H-3,1-benzoxazine-4-oneof the formula:

2-[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-5,8-dichloro-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.57 (1H, s), 7.62 (1H, d, J=8 Hz) 7.72(1H, dd, J=8 Hz, 4 Hz), 7.87 (1H, d, J=8 Hz), 8.31 (1H, d, J=8 Hz), 8.59(1H, d, J=4 Hz).

REFERENCE PREPARATION EXAMPLE 66-(1)

According to the same manner as that of Reference Preparation Example63-(1), 5-chloro-2-methylaniline was used in place of3-chloro-2-methylaniline to obtainN-(5-chloro-2-methylphenyl)-2-(hydroxyimino)acetamide of the formula:

N-(5-Chloro-2-methylphenyl)-2-(hydroxyimino)acetamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.20 (3H, s), 7.17 (1H, dd, J=8 Hz, 2Hz), 7.27 (1H, d, J=8 Hz), 7.64 (1H, d, J=2 Hz), 7.70 (1H, d, J=2 Hz),9.56 (1H, s), 12.27 (1H, s).

REFERENCE PREPARATION EXAMPLE 66-(2)

According to the same manner as that of Reference Preparation Example63-(2), N-(5-chloro-2-methylphenyl)-2-(hydroxyimino)acetamide was usedin place of N-(3-chloro-2-methylphenyl)-2-(hydroxyimino)acetamide toobtain 4-chloro-7-methyl-1H-indole-2,3-dione of the formula:

4-Chloro-7-methyl-1H-indole-2,3-dione

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.16 (3H, s), 6.99 (1H, d, J=8 Hz) 7.40(1H, d, J=8 Hz), 11.24 (1H, s).

REFERENCE PREPARATION EXAMPLE 66-(3)

According to the same manner as that of Reference Preparation Example63-(3), 4-chloro-7-methyl-1H-indole-2,3-dione was used in place of6-chloro-7-methyl-1H-indole-2,3-dione to obtain2-amino-6-chloro-3-methylbenzoic acid of the formula:

2-Amino-6-chloro-3-methylbenzoic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.07 (3H, s), 6.57 (1H, d, J=8 Hz), 7.01(1H, d, J=8 Hz).

REFERENCE PREPARATION EXAMPLE 66-(4)

According to the same manner as that of Reference Preparation Example46-(1), 2-amino-6-chloro-3-methylbenzoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-5-chloro-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-5-chloro-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.66 (3H, s), 7.52-7.56 (2H, m), 7.62(1H, d, J=8 Hz), 7.76 (1H, dd, J=8 Hz, 4 Hz), 8.34 (1H, d, J=8 Hz), 8.63(1H, d, J=4 Hz).

REFERENCE PREPARATION EXAMPLE 67-(1)

To a mixture of 5 g of 4-ethoxy-1,1,1-trifluoro-3-butene-2-one, 3 g ofsodium acetate and 15 ml of ethanol was added 4.6 g oftert-butylhydrazine hydrochloride, and the mixture was heated to refluxfor 2 days. Water was added to the reaction mixture, and the mixture wasextracted with diethyl ether three times. The organic layers werecombined, washed with an aqueous saturated sodium chloride solution,dried over anhydrous magnesium sulfate, and concentrated under reducedpressure to obtain 3.0 g of 1-tert-butyl-3-trifluoromethyl-1H-pyrazoleof the formula:

1-tert-Butyl-3-trifluoromethyl-1H-pyrazole

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.61 (9H, s), 6.48 (1H, d, J=2 Hz), 7.54(1H, d, J=2 Hz).

REFERENCE PREPARATION EXAMPLE 67-(2)

According to the same manner as that of Reference Preparation Example18, 1-tert-butyl-3-trifluoromethyl-1H-pyrazole was used in place of1-methyl-3-trifluoromethyl-1H-pyrazole to obtain1-tert-butyl-3-trifluoromethyl-1H-pyrazole-5-carboxylic acid of theformula:

1-tert-Butyl-3-trifluoromethyl-1H-pyrazole-5-carboxylic Acid

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.75 (9H, s), 7.28 (1H, s).

REFERENCE PREPARATION EXAMPLE 67-(3)

According to the same manner as that of Reference Preparation Example13, 1-tert-butyl-3-trifluoromethyl-1H-pyrazole-5-carboxylic acid wasused in place of 1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acidto obtain6-chloro-2-(1-tert-butyl-3-trifluoromethyl-1H-pyrazol-5-yl)-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-(1-tert-butyl-3-trifluoromethyl-1H-pyrazol-5-yl)-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.86 (9H, s), 2.61 (3H, s), 7.32 (1H, s),7.68 (1H, d, J=2 Hz), 8.08 (1H, d, J=2 Hz).

REFERENCE PREPARATION EXAMPLE 67-(4)

According to the same manner as that of Reference Preparation Example 1,6-chloro-2-(1-tert-butyl-3-trifluoromethyl-1H-pyrazol-5-yl)-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-tert-butyl)-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-tert-butyl-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.67 (9H, s), 2.27 (3H, s), 4.36 (2H, s),7.11 (1H, s), 7.34 (1H, s), 7.48 (1H, s), 9.63 (1H, brs), 10.22 (1H,brs).

REFERENCE PREPARATION EXAMPLE 68-(1)

According to the same manner as that of Reference Preparation Example24, tert-butylhydrazine hydrochloride was used in place of2-chlorophenylhydrazine hydrochloride to obtain1-tert-butyl-3-(2-furyl)-5-trifluoromethyl-1H-pyrazole of the formula:

1-tert-Butyl-3-(2-furyl)-5-trifluoromethyl-1H-pyrazole

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.53 (9H, s), 6.48-6.51 (2H, m) 6.59 (1H,s), 7.55 (1H, dd, J=2 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 68-(2)

According to the same manner as that of Reference Preparation Example25, 1-tert-butyl-3-(2-furyl)-5-trifluoromethyl-1H-pyrazole was used inplace of 1-(2-chlorophenyl)-5-(2-furyl)-3-trifluoromethyl-1H-pyrazole toobtain 1-tert-butyl-5-trifluoromethyl-1H-pyrazole-3-carboxylic acid ofthe formula:

1-tert-Butyl-5-trifluoromethyl-1H-pyrazole-3-carboxylic Acid

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.73 (9H, s), 7.90 (1H, brs).

REFERENCE PREPARATION EXAMPLE 68-(3)

According to the same manner as that of Reference Preparation Example13, 1-tert-butyl-5-trifluoromethyl-1H-pyrazole-3-carboxylic acid wasused in place of 1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acidto obtain6-chloro-2-[1-tert-butyl-5-trifluoromethyl-1H-pyrazol-3-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[1-tert-butyl-5-trifluoromethyl-1H-pyrazol-3-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.76 (9H, s), 2.58 (3H, s), 7.57 (1H, s),7.74 (1H, d, J=2 Hz), 8.12 (1H, d, J=2 Hz).

REFERENCE PREPARATION EXAMPLE 68-(4)

According to the same manner as that of Reference Preparation Example 1,6-chloro-2-(1-tert-butyl-5-trifluoromethyl-1H-pyrazol-3-yl)-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-tert-butyl-5-trifluoromethyl-1H-pyrazole-3-carboxamideof the formula:

N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-tert-butyl-5-trifluoromethyl-1H-pyrazole-3-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.70 (9H, s), 2.26 (3H, s), 4.39 (2H, s),7.37 (1H, s), 7.50 (1H, s), 7.85 (1H, s), 9.75 (1H, brs), 10.67 (1H,brs).

REFERENCE PREPARATION EXAMPLE 69

According to the same manner as that of Reference Preparation Example46-(1), 2-amino-3-methylbenzoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.74 (3H, s), 7.46-7.51 (2H, m), 7.68(1H, d, J=8 Hz), 7.76 (1H, dd, J=8 Hz, 4 Hz), 7.94 (1H, d, J=8 Hz), 8.35(1H, dd, J=8 Hz, 1Hz), 8.63 (1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 70

According to the same manner as that of Reference Preparation Example46-(1), 2-amino-3-bromobenzoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain8-bromo-2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-4H-3,1-benzoxazine-4-one of the formula:

8-Bromo-2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.49 (1H, t, J=8 Hz), 7.54 (1H, s), 7.72(1H, dd, J=8 Hz, 4 Hz), 8.08 (1H, s), 8.10 (1H, s), 8.32 (1H, t, J=4Hz), 8.60 (1H, d, J=4 Hz).

REFERENCE PREPARATION EXAMPLE 71-(1)

A mixture of 1.0 g of pyrrole, 3.0 g of3-chloro-2-methanesulfonylpyridine, 6.6 g of cesium carbonate and 10 mlof N,N-dimethylformamide was stirred at 60° C. for 27 hours. After thereaction mixture was allowed to cool to room temperature, water waspoured and the mixture was extracted with ethyl acetate two times. Theorganic layers were combined, washed successively with water and anaqueous saturated sodium chloride solution, dried over magnesiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel column chromatography to obtain 1.7 g of3-chloro-2-(1H-pyrrol-1-yl)pyridine of the formula:

3-Chloro-2-(1H-pyrrol-1-yl)pyridine

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.35 (2H, t, J=2 Hz), 7.15 (1H, dd, J=8 Hz,5 Hz), 7.42 (2H, t, J=2 Hz), 7.83 (1H, dd, J=8 Hz, 2 Hz), 8.39 (1H, dd,J=5 Hz, 2 Hz).

REFERENCE PREPARATION EXAMPLE 71-(2)

To 3.8 ml of N,N-dimethylformamide was added dropwise 4.2 ml ofphosphorus oxychloride at room temperature, and the mixture was stirredat room temperature for 30 minutes. Thereto 1.6 g of3-chloro-2-(1H-pyrrol-1-yl)pyridine was added, and the resulting mixturewas stirred at 60° C. for 2 hours. The reaction mixture was allowed tocool to room temperature, and then slowly added to ice-water. Themixture was adjusted to pH 4 by an addition of a 2N aqueous sodiumhydroxide solution. A deposited precipitate was collected by filtrationto obtain 1.7 g of 3-chloro-2-(2-formyl-1H-pyrrol-1-yl)pyridine of theformula:

3-Chloro-2-(2-formyl-1H-pyrrol-1-yl)pyridine

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.48 (1H, dd, J=4 Hz, 3 Hz), 7.14-7.15 (2H,m), 7.39 (1H, dd, J=8 Hz, 5 Hz), 7.89 (1H, dd, J=8 Hz, 2 Hz), 8.47 (1H,dd, J=5 Hz, 2 Hz), 9.57 (1H, d, J=1 Hz).

REFERENCE PREPARATION EXAMPLE 71-(3)

To a solution of 1.5 g of 3-chloro-2-(2-formyl-1H-pyrrol-1-yl)pyridinein 20 ml of N,N-dimethylformamide, 1.3 g of N-bromosuccinimide wasadded. The mixture was stirred at room temperature for 3 hours. Waterwas poured into the reaction mixture, and a deposited precipitate wascollected by filtration to obtain 1.9 g of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde of theformula:

4-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.11 (1H, d, J=2 Hz), 7.14 (1H, dd, J=2 Hz,1Hz), 7.41 (1H, dd, J=8 Hz, 5 Hz), 7.89 (1H, dd, J=8 Hz, 2 Hz), 8.46(1H, dd, J=5 Hz, 2 Hz), 9.51 (1H, d, J=1 Hz).

REFERENCE PREPARATION EXAMPLE 71-(4)

An aqueous solution of 1.2 g of potassium permanganate in 10 ml of waterwas added dropwise to a mixture of 0.72 g of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde and 15 ml ofacetone while the mixture was retained at 40° C. The mixture was thenstirred at 60° C. for 8 hours. Precipitates were filtered off to obtaina filtrate. The filtrate was adjusted to pH 10-12 by an addition of a 2Naqueous sodium hydroxide solution, and then washed with chloroform twotimes. The aqueous layer was adjusted to around pH 3 by an addition of2N hydrochloric acid. A deposited precipitate was collected byfiltration to obtain 0.56 g of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid of theformula:

4-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 6.99 (1H, d, J=2 Hz), 7.38 (1H, d, J=2Hz), 7.56 (1H, dd, J=8 Hz, 5 Hz), 8.10 (1H, dd, J=8 Hz, 2 Hz), 8.48 (1H,dd, J=5 Hz, 2 Hz).

REFERENCE PREPARATION EXAMPLE 71-(5)

A mixture of 0.56 g of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid and 0.40ml of thionyl chloride was heated to reflux in acetonitrile for 2 hours.The reaction mixture was allowed to cool to room temperature, and thenconcentrated under reduced pressure. The resulting residue was dissolvedin 10 ml of acetonitrile. Thereto 0.35 g of2-amino-5-chloro-3-methylbenzoic acid was added, and the resultingmixture was stirred at room temperature for 10 minutes. To the mixture,0.53 ml of pyridine was added, and the mixture was stirred at roomtemperature for 6 hours. Then 0.19 ml of methanesulfonyl chloride wasadded, and the mixture was stirred at room temperature for 1 hour. Waterwas poured into the reaction mixture, and a deposited precipitate wascollected by filtration to obtain 0.29 g of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[4-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.73 (3H, s), 7.07 (1H, d, J=2 Hz), 7.32(1H, d, J=2 Hz), 7.42-7.44 (2H, m), 7.91 (1H, dd, J=8 Hz, 2 Hz), 7.93(1H, d, J=2 Hz), 8.51 (1H, dd, J=5 Hz, 2 Hz).

REFERENCE PREPARATION EXAMPLE 71-(6)

A mixture of 0.29 g of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one,0.10 g of hydrazine monohydrate and 10 ml of tetrahydrofuran was stirredat room temperature for 2 hours. Water was added to the reactionmixture, and the mixture was extracted with ethyl acetate three times.The organic layers were combined, washed with an aqueous saturatedsodium chloride solution, dried over anhydrous magnesium sulfate, andconcentrated under reduced pressure to obtain 0.30 g of4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

4-Bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.20 (3H, s), 4.04 (2H, brs), 7.02 (1H, d,J=2 Hz), 7.04 (1H, d, J=2 Hz), 7.21 (1H, d, J=2 Hz), 7.28 (1H, d, J=2Hz), 7.31 (1H, dd, J=8 Hz, 5 Hz), 7.34 (1H, brs), 7.80 (1H, dd, J=8 Hz,2 Hz), 8.41 (1H, dd, J=5 Hz, 2 Hz), 9.27 (1H, brs)

REFERENCE PREPARATION EXAMPLE 72

A mixture of 0.60 g of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one,0.29 g of isopropylhydrazine hydrochloride, 0.27 g of triethylamine and6 ml of tetrahydrofuran was stirred at room temperature for 3 hours.Water was poured into the reaction mixture, and the mixture wasextracted with ethyl acetate two times. The combined organic layer waswashed with an aqueous saturated sodium chloride solution, dried overanhydrous magnesium sulfate, and concentrated under reduced pressure.The residue was subjected to silica gel column chromatography to obtain0.35 g of3-bromo-N-[4-chloro-2-(N′-isopropylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideof the formula:

3-Bromo-N-[4-chloro-2-(N′-isopropylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.08 (6H, d, J=6 Hz), 2.11 (3H, s), 3.12(1H, hept., J=6 Hz), 4.60 (1H, brs), 7.11 (1H, s), 7.14 (1H, d, J=2 Hz),7.20 (1H, d, J=2 Hz), 7.37 (1H, dd, J₁=8 Hz, J₂=4 Hz), 7.79 (1H, brs),7.84 (1H, dd, J₁=8 Hz, J₂=1 Hz), 8.44 (1H, dd, J=4 Hz, 1Hz), 9.93 (1H,brs).

REFERENCE PREPARATION EXAMPLE 73-(1)

According to the same manner as that of Reference Preparation Example20, N-iodosuccinimide was used in place of1,2-dibromo-1,1,2,2-tetrachloroethane to obtainN,N-dimethyl-5-iodo-1H-pyrazole-1-sulfonamide of the formula:

N,N-dimethyl-5-iodo-1H-pyrazole-1-sulfonamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.07 (6H, s), 6.60 (1H, d, J=1 Hz), 7.62(1H, d, J=1 Hz)

REFERENCE PREPARATION EXAMPLE 73-(2)

According to the same manner as that of Reference Preparation Example21, N,N-dimethyl-5-iodo-1H-pyrazole-1-sulfonamide was used in place of5-bromo-N,N-dimethyl-1H-pyrazole-1-sulfonamide to obtain3-iodo-1H-pyrazole of the formula:

3-Iodo-1H-pyrazole

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.74 (1H, d, J=3 Hz), 8.10 (1H, d, J=3 Hz).

REFERENCE PREPARATION EXAMPLE 73-(3)

According to the same manner as that of Reference Preparation Example22, 3-iodo-1H-pyrazole was used in place of 3-bromo-1H-pyrazole toobtain 3-chloro-2-(3-iodo-1H-pyrazol-1-yl)pyridine of the formula:

3-Chloro-2-(3-iodo-1H-pyrazol-1-yl)pyridine

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.65 (1H, d, J=2 Hz), 7.31 (1H, dd, J=8 Hz,4 Hz), 7.91 (1H, dd, J=8 Hz, 1Hz), 7.95 (1H, d, J=2 Hz), 8.46 (1H, dd,J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 73-(4)

According to the same manner as that of Reference Preparation Example23, 3-chloro-2-(3-iodo-1H-pyrazol-1-yl)pyridine was used in place of2-(3-bromo-1H-pyrazol-1-yl)-3-chloropyridine to obtain1-(3-chloro-2-pyridinyl)-3-iodo-1H-pyrazole-5-carboxylic acid of theformula:

1-(3-Chloro-2-pyridinyl)-3-iodo-1H-pyrazole-5-carboxylic Acid

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.20 (1H, s), 7.44 (1H, dd, J=8 Hz, 4 Hz),7.91 (1H, dd, J=8 Hz, 1Hz), 8.50 (1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 73-(5)

According to the same manner as that of Reference Preparation Example13, 1-(3-chloro-2-pyridinyl)-3-iodo-1H-pyrazole-5-carboxylic acid wasused in place of 1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acidto obtain6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-iodo-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[1-(3-chloro-2-pyridinyl)-3-iodo-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.82 (3H, s), 7.39 (1H, s), 7.47-7.50 (2H,m), 7.95-7.98 (2H, m), 8.56 (1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 73-(6)

According to the same manner as that of Reference Preparation Example 7,6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-iodo-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-iodo-1H-pyrazole-5-carboxamideof the formula:

N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-iodo-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆) δ (ppm): 2.13 (3H, s), 4.36 (2H, brs), 7.31 (1H, brs),7.42 (1H, brs), 7.46 (1H, brs), 7.59 (1H, dd, J=8 Hz, 4 Hz), 8.15 (1H,d, J=8 Hz), 8.49 (1H, dd, J=4 Hz, 1Hz), 9.54 (1H, brs), 10.20 (1H, brs).

REFERENCE PREPARATION EXAMPLE 74-(1)

According to the same manner as that of Reference Preparation Example22, 4-bromo-1H-pyrazole was used in place of 3-bromo-1H-pyrazole toobtain 2-(4-bromo-1H-pyrazol-1-yl)-3-chloropyridine of the formula:

2-(4-Bromo-1H-pyrazol-1-yl)-3-chloropyridine

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.31 (1H, dd, J=8 Hz, 4 Hz), 7.77 (1H, s),7.92 (1H, dd, J=8 Hz, 1Hz), 8.19 (1H, s), 8.45 (1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 74-(2)

According to the same manner as that of Reference Preparation Example23, 2-(4-bromo-1H-pyrazol-1-yl)-3-chloropyridine was used in place of2-(3-bromo-1H-pyrazol-1-yl)-3-chloropyridine to obtain4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid of theformula:

4-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic Acid

¹H-NMR (DMSO-d₆) δ (ppm): 7.66 (1H, dd, J=8 Hz, 4 Hz), 8.06 (1H, s),8.23 (1H, dd, J=8 Hz, 1Hz), 8.54 (1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 74-(3)

According to the same manner as that of Reference Preparation Example13, 4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid wasused in place of 1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acidto obtain2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[4-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.00 (3H, s), 7.46 (1H, dd, J=8 Hz, 4 Hz),7.53 (1H, d, J=2 Hz), 7.87 (1H, s), 7.95 (1H, dd, J=8 Hz, 1Hz), 7.98(1H, d, J=2 Hz), 8.51 (1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 74-(4)

According to the same manner as that of Reference Preparation Example 7,2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtain4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideof the formula:

4-Bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆) δ (ppm): 2.13 (3H, s), 4.47 (2H, brs), 7.37 (1H, s),7.48 (1H, s), 7.62 (1H, dd, J=8 Hz, 4 Hz), 8.12 (1H, s), 8.19 (1H, d,J=8 Hz), 8.50 (1H, d, J=4 Hz), 9.69 (1H, brs), 10.24 (1H, brs).

REFERENCE PREPARATION EXAMPLE 75-(1)

According to the same manner as that of Reference Preparation Example22, 3-phenyl-1H-pyrazole was used in place of 3-bromo-1H-pyrazole toobtain 3-chloro-2-(3-phenyl-1H-pyrazol-1-yl)pyridine of the formula:

3-Chloro-2-(3-phenyl-1H-pyrazol-1-yl)pyridine

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.82 (1H, d, J=2 Hz), 7.27 (1H, dd, J=8 Hz,4 Hz), 7.35 (1H, m), 7.43 (2H, m), 7.93 (3H, m), 8.20 (1H, d, J=2 Hz),8.48 (1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 75-(2)

According to the same manner as that of Reference Preparation Example23, 3-chloro-2-(3-phenyl-1H-pyrazol-1-yl)pyridine was used in place of2-(3-bromo-1H-pyrazol-1-yl)-3-chloropyridine to obtain1-(3-chloro-2-pyridinyl)-3-phenyl-1H-pyrazole-5-carboxylic acid of theformula:

1-(3-Chloro-2-pyridinyl)-3-phenyl-1H-pyrazole-5-carboxylic Acid

¹H-NMR (DMSO-d₆) δ (ppm): 7.36-7.45 (3H, m), 7.57 (1H, s), 7.67 (1H, dd,J=8 Hz, 4 Hz), 7.90-7.92 (2H, m), 8.24 (1H, dd, J=8 Hz, 1Hz), 8.57 (1H,dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 75-(3)

According to the same manner as that of Reference Preparation Example13, 1-(3-chloro-2-pyridinyl)-3-phenyl-1H-pyrazole-5-carboxylic acid wasused in place of 1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acidto obtain6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-phenyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[1-(3-chloro-2-pyridinyl)-3-phenyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.83 (3H, s), 7.39-7.52 (5H, m), 7.59 (1H,s), 7.92-8.00 (4H, m), 8.59 (1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 75-(4)

According to the same manner as that of Reference Preparation Example 7,6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-phenyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-phenyl-1H-pyrazole-5-carboxamideof the formula:

N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-phenyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆) δ (ppm): 2.19 (3H, s), 4.40 (2H, brs), 7.33 (1H, d, J=2Hz), 7.42-7.92 (4H, m), 7.60 (1H, dd, J=8 Hz, 4 Hz), 7.70 (1H, s), 7.88(2H, d, J=7 Hz), 8.17 (1H, d, J=8 Hz), 8.53 (1H, d, J=4 Hz), 9.58 (1H,brs), 10.27 (1H, brs).

REFERENCE PREPARATION EXAMPLE 76-(1)

To a mixture of 4.0 g of N,N-dimethyl-1H-pyrazole-1-sulfonamide and 45ml of tetrahydrofuran was added dropwise 15.7 ml of a 1.6M n-butyllithium solution in hexane at −78° C., and the mixture was stirred at−78° C. for 10 minutes. After 2.3 ml of dimethyl disulfide was added tothe mixture, the mixture was stirred for 4 hours while the reactiontemperature was gradually returned to room temperature. Water was pouredinto the reaction mixture, and the mixture was extracted with methylt-butyl ether three times. The combined organic layer was washedsuccessively with a 1N aqueous sodium hydroxide solution and an aqueoussaturated sodium chloride solution, dried over magnesium sulfate, andconcentrated under reduced pressure. The resulting residue was subjectedto silica gel column chromatography to obtain 4.87 g ofN,N-dimethyl-5-methylthio-1H-pyrazole-1-sulfonamide of the formula:

N,N-dimethyl-5-methylthio-1H-pyrazole-1-sulfonamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.49 (3H, s), 3.01 (6H, s), 6.10 (1H, d,J=2 Hz), 7.63 (1H, d, J=2 Hz).

REFERENCE PREPARATION EXAMPLE 76-(2)

According to the same manner as that of Reference Preparation Example21, N,N-dimethyl-5-methylthio-1H-pyrazole-1-sulfonamide was used inplace of 5-bromo-N,N-dimethyl-1H-pyrazole-1-sulfonamide to obtain3-methylthio-1H-pyrazole of the formula:

3-Methylthio-1H-pyrazole

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.61 (3H, s), 6.45 (1H, d, J=3 Hz), 8.19(1H, d, J=3 Hz).

REFERENCE PREPARATION EXAMPLE 76-(3)

According to the same manner as that of Reference Preparation Example22, 3-methylthio-1H-pyrazole was used in place of 3-bromo-1H-pyrazole toobtain 3-chloro-2-(3-methylthio-1H-pyrazol-1-yl)pyridine of the formula:

3-Chloro-2-(3-methylthio-1H-pyrazol-1-yl)pyridine

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.61 (3H, s), 6.40 (1H, d, J=2 Hz), 7.25(1H, dd, J=8 Hz, 4 Hz), 7.89 (1H, dd, J=8 Hz, 1Hz), 8.12 (1H, d, J=2Hz), 8.43 (1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 76-(4)

According to the same manner as that of Reference Preparation Example23, 3-chloro-2-(3-methylthio-1H-pyrazol-1-yl)pyridine was used in placeof 2-(3-bromo-1H-pyrazol-1-yl)-3-chloropyridine to obtain1-(3-chloro-2-pyridinyl)-3-methylthio-1H-pyrazole-5-carboxylic acid ofthe formula:

1-(3-Chloro-2-pyridinyl)-3-methylthio-1H-pyrazole-5-carboxylic Acid

¹H-NMR (DMSO-d₆) δ (ppm): 2.49 (3H, s), 7.02 (1H, s), 7.62 (1H, dd, J=8Hz, 4 Hz), 8.19 (1H, dd, J=8 Hz, 1Hz), 8.51 (1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 76-(5)

According to the same manner as that of Reference Preparation Example13, 1-(3-chloro-2-pyridinyl)-3-methylthio-1H-pyrazole-5-carboxylic acidwas used in place of 1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylicacid to obtain6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-methylthio-1H-pyrazole-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[1-(3-chloro-2-pyridinyl)-3-methylthio-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.81 (3H, s), 2.61 (3H, s), 7.15 (1H, s),7.45-7.48 (2H, m), 7.94-7.98 (2H, m), 8.56 (1H, d, J=4 Hz).

REFERENCE PREPARATION EXAMPLE 76-(6)

According to the same manner as that of Reference Preparation Example 7,6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-methylthio-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-methylthio-1H-pyrazole-5-carboxamideof the formula:

N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-methylthio-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆) δ (ppm): 2.14 (3H, s), 2.53 (3H, s), 4.37 (2H, brs),7.20 (1H, s), 7.30 (1H, s), 7.46 (1H, s), 7.56 (1H, dd, J=8 Hz, 4 Hz),8.12 (1H, d, J=8 Hz), 8.47 (1H, d, J=4 Hz), 9.54 (1H, brs), 10.16 (1H,brs).

REFERENCE PREPARATION EXAMPLE 77-(1)

To a mixture of 0.50 g of1-(3-chloro-2-pyridinyl)-3-methylthio-1H-pyrazole-5-carboxylic acid and5 ml of trifluoroacetic acid was added 0.4 ml of 30% aqueous hydrogenperoxide, and the resulting mixture was stirred at room temperature for4 hours. Water was poured into the reaction mixture, and the mixture wasextracted with methyl t-butyl ether three times. The combined organiclayer was washed with an aqueous saturated sodium chloride solution,dried over anhydrous sodium sulfate, and concentrated under reducedpressure to obtain 0.44 g of1-(3-chloro-2-pyridinyl)-3-methylsulfonyl-1H-pyrazole-5-carboxylic acidof the formula:

1-(3-Chloro-2-pyridinyl)-3-methylsulfonyl-1H-pyrazole-5-carboxylic Acid

¹H-NMR (DMSO-d₆) δ (ppm): 3.39 (3H, s), 7.57 (1H, s), 7.75 (1H, dd, J=8Hz, 4 Hz), 8.31 (1H, dd, J=8 Hz, 1Hz), 8.61 (1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 77-(2)

According to the same manner as that of Reference Preparation Example13, 1-(3-chloro-2-pyridinyl)-3-methylsulfonyl-1H-pyrazole-5-carboxylicacid was used in place of1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid to obtain6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-methylsulfonyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[1-(3-chloro-2-pyridinyl)-3-methylsulfonyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.85 (3H, s), 3.30 (3H, s), 7.52-7.57 (2H,m), 7.72 (1H, s), 7.99-8.03 (2H, m), 8.58 (1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 78

To a mixture of 0.20 g of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-methylthio-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one,5 ml of dichloromethane and 0.5 ml of water was added 0.18 g ofmagnesium bis(monoperoxophthalate) hexahydrate (MMPP), and the resultingmixture was stirred at room temperature for 22 hours. Water was added tothe reaction mixture, and the mixture was extracted with methyl t-butylether. The organic layer was washed with water and an aqueous saturatedsodium chloride solution, dried over anhydrous magnesium sulfate, andconcentrated under reduced pressure to obtain 0.20 g of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-methylsulfinyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[1-(3-chloro-2-pyridinyl)-3-methylsulfinyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.85 (3H, s), 3.04 (3H, s), 7.52-7.55 (2H,m), 7.74 (1H, s), 7.99-8.01 (2H, m), 8.58 (1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 79-(1)

A mixture of 2.5 g of ethyl 2,4-dioxovalerate, 1.45 g ofO-methylhydroxylamine hydrochloride and 10 ml of ethanol was heated toreflux for 2 hours. The reaction mixture was allowed to cool to roomtemperature, and partitioned between water and ethyl acetate. Theorganic layer was washed with water and an aqueous saturated sodiumchloride solution, dried over anhydrous magnesium sulfate, andconcentrated under reduced pressure. The residue was subjected to silicagel column chromatography to obtain 1.34 g of ethyl2-methoxyimino-4-oxopentanoate of the formula:

Ethyl 2-methoxyimino-4-oxopentanoate

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.35 (3H, t, J=7 Hz), 2.21 (3H, s), 3.71(2H, s), 4.07 (3H, s), 4.34 (2H, q, J=7 Hz).

REFERENCE PREPARATION EXAMPLE 79-(2)

A mixture of 1.34 g of ethyl 2-methoxyimino-4-oxopentanoate, 1.23 g of3-chloro-2-hydrazinopyridine, 25 ml of tetrahydrofuran and 50 ml ofacetic acid was heated to reflux for 8 hours. The reaction mixture wasconcentrated under reduced pressure. Water was poured into the residue,and the mixture was extracted with methyl t-butyl ether two times. Thecombined organic layer was washed successively with a 1N aqueous sodiumhydroxide solution, water and an aqueous saturated sodium chloridesolution, dried over anhydrous magnesium sulfate, and concentrated underreduced pressure. The residue was subjected to silica gel columnchromatography to obtain 0.30 g of ethyl1-(3-chloro-2-pyridinyl)-3-methyl-1H-pyrazole-5-carboxylate of theformula:

Ethyl 1-(3-chloro-2-pyridinyl)-3-methyl-1H-pyrazole-5-carboxylate

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.20 (3H, t, J=7 Hz), 2.40 (3H, s), 4.20(2H, q, J=7 Hz), 6.84 (1H, s), 7.40 (1H, dd, J=8 Hz, 4 Hz), 7.88 (1H, d,J=8 Hz), 8.51 (1H, d, J=4 Hz)

REFERENCE PREPARATION EXAMPLE 79-(3)

A mixture of 0.30 g of ethyl1-(3-chloro-2-pyridinyl)-3-methyl-1H-pyrazole-5-carboxylate, 5 ml ofmethanol and 5 ml of a 2N aqueous sodium hydroxide solution was heatedto reflux for 3 hours. After the reaction mixture was allowed to cool,water was poured and the aqueous layer was washed with methyl t-butylether two times. The aqueous layer was adjusted to around pH 3 by anaddition of 2N hydrochloric acid, and then extracted with methyl t-butylether three times. The combined organic layer was washed with an aqueoussaturated sodium chloride solution, dried over anhydrous magnesiumsulfate, and concentrated under reduced pressure to obtain 0.24 g of1-(3-chloro-2-pyridinyl)-3-methyl-1H-pyrazole-5-carboxylic acid of theformula:

1-(3-Chloro-2-pyridinyl)-3-methyl-1H-pyrazole-5-carboxylic Acid

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.40 (3H, s), 6.89 (1H, s), 7.40 (1H, dd,J=8 Hz, 4 Hz), 7.89 (1H, dd, J=8 Hz, 1Hz), 8.49 (1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 79-(4)

According to the same manner as that of Reference Preparation Example13, 1-(3-chloro-2-pyridinyl)-3-methyl-1H-pyrazole-5-carboxylic acid wasused in place of 1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acidto obtain6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-methyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[1-(3-chloro-2-pyridinyl)-3-methyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.81 (3H, s), 2.45 (3H, s), 7.07 (1H, s),7.43-7.47 (2H, m), 7.92-7.98 (2H, m), 8.56 (1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 80-(1)

To a mixture of 17.2 g of 3-methyl-2-butanone, 27.1 g of diethyl oxalateand 130 ml of ethanol was added 95 ml of sodium ethoxide (20% ethanolsolution), and the resulting mixture was stirred at 60° C. for 5 hours.After allowed to cool to room temperature, a deposited precipitate wascollected by filtration and washed with ethanol. The filter cake waspartitioned between 2N hydrochloric acid and methyl t-butyl ether. Theorganic layer was washed with an aqueous saturated sodium chloridesolution, dried over anhydrous magnesium sulfate, and concentrated underreduced pressure to obtain 28.8 g of ethyl4-hydroxy-5-methyl-2-oxo-3-hexenoate of the formula:

Ethyl 4-hydroxy-5-methyl-2-oxo-3-hexenoate

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.19 (6H, d, J=7 Hz), 1.38 (3H, t, J=7 Hz),2.66 (1H, hept., J=7 Hz), 4.36 (2H, q, J=7 Hz), 6.41 (1H, s).

REFERENCE PREPARATION EXAMPLE 80-(2)

A mixture of 5.0 g of ethyl 4-hydroxy-5-methyl-2-oxo-3-hexenoate, 2.46 gof O-methylhydroxylamine hydrochloride and 10 ml of ethanol was stirredat room temperature for 6 hours. After ethyl acetate was poured into thereaction mixture, the organic layer was washed with water and an aqueoussaturated sodium chloride solution, dried over anhydrous magnesiumsulfate, and concentrated under reduced pressure to obtain 5.32 g ofethyl 2-methoxyimino-5-methyl-4-oxohexanoate of the formula:

Ethyl 2-methoxyimino-5-methyl-4-oxohexanoate

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.15 (6H, d, J=7 Hz), 1.34 (3H, t, J=7 Hz),2.68 (1H, hept., J=7 Hz), 3.76 (2H, s), 4.05 (3H, s), 4.33 (2H, q, J=7Hz).

REFERENCE PREPARATION EXAMPLE 80-(3)

A mixture of 3.0 g of ethyl 2-methoxyimino-5-methyl-4-oxohexanoate, 2.4g of 3-chloro-2-hydrazinopyridine, 50 ml of tetrahydrofuran and 100 mlof acetic acid was stirred at room temperature for 20 hours, and thenheated to reflux for 4 hours. The reaction mixture was concentratedunder reduced pressure. Water was poured into the residue, and themixture was extracted with methyl t-butyl ether two times. The combinedorganic layer was washed successively with a 1N aqueous sodium hydroxidesolution, water and an aqueous saturated chloride solution, dried overanhydrous magnesium sulfate, and concentrated under reduced pressure.The residue was subjected to silica gel column chromatography to obtain1.07 g of ethyl1-(3-chloro-2-pyridinyl)-3-isopropyl-1H-pyrazole-5-carboxylate of theformula:

Ethyl 1-(3-chloro-2-pyridinyl)-3-isopropyl-1H-pyrazole-5-carboxylate

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.20 (3H, t, J=7 Hz), 1.34 (6H, d, J=7 Hz),3.11 (1H, hept., J=7 Hz), 4.20 (2H, q, J=7 Hz), 6.88 (1H, s), 7.40 (1H,dd, J=8 Hz, 4 Hz), 7.88 (1H, d, J=8 Hz), 8.52 (1H, d, J=4 Hz).

REFERENCE PREPARATION EXAMPLE 80-(4)

A mixture of 1.07 g of ethyl1-(3-chloro-2-pyridinyl)-3-isopropyl-1H-pyrazole-5-carboxylate, 15 ml ofmethanol and 15 ml of a 2N aqueous sodium hydroxide solution was heatedto reflux for 1.5 hours. After the reaction mixture was allowed to cool,water was poured and the mixture was washed with methyl t-butyl ethertwo times. The aqueous layer was adjusted to around pH 3 by an additionof 2N hydrochloric acid, and then extracted with methyl t-butyl etherthree times. The combined organic layer was washed with an aqueoussaturated sodium chloride solution, dried over anhydrous magnesiumsulfate, and concentrated under reduced pressure to obtain 0.97 g of1-(3-chloro-2-pyridinyl)-3-isopropyl-1H-pyrazole-5-carboxylic acid ofthe formula:

1-(3-Chloro-2-pyridinyl)-3-isopropyl-1H-pyrazole-5-carboxylic Acid

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.33 (6H, d, J=7 Hz), 3.10 (1H, hept., J=7Hz), 6.93 (1H, s), 7.39 (1H, dd, J=8 Hz, 4 Hz), 7.88 (1H, d, J=8 Hz),8.49 (1H, d, J=4 Hz).

REFERENCE PREPARATION EXAMPLE 80-(5)

According to the same manner as that of Reference Preparation Example13, 1-(3-chloro-2-pyridinyl)-3-isopropyl-1H-pyrazole-5-carboxylic acidwas used in place of 1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylicacid to obtain6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-isopropyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[1-(3-chloro-2-pyridinyl)-3-isopropyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.37 (6H, d, J=7 Hz), 1.81 (3H, s), 3.15(1H, hept., J=7 Hz), 7.12 (1H, s), 7.45 (1H, dd, J=8 Hz, 4 Hz), 7.47(1H, d, J=1 Hz), 7.93 (1H, dd, J=8 Hz, 1Hz), 7.98 (1H, d, J=1 Hz), 8.56(1H, dd, J=4 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 81

According to the same manner as that of Reference Preparation Example46, 1-(3-chloro-2-pyridinyl)-3-isopropyl-1H-pyrazole-5-carboxylic acidwas used in place of3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid to obtain2-[1-(3-chloro-2-pyridinyl)-3-isopropyl-1H-pyrazol-5-yl]-6,8-dibromo-4H-3,1-benzoxazine-4-oneof the formula:

2-[1-(3-Chloro-2-pyridinyl)-3-isopropyl-1H-pyrazol-5-yl]-6,8-dibromo-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.35 (6H, d, J=7 Hz), 3.16 (1H, hept., J=7Hz), 7.16 (1H, s), 7.43 (1H, dd, J=8 Hz, 4 Hz), 7.94 (1H, dd, J=8 Hz,1Hz), 8.03 (1H, d, J=2 Hz), 8.25 (1H, d, J=2 Hz), 8.56 (1H, dd, J=4 Hz,1Hz).

REFERENCE PREPARATION EXAMPLE 82-(1)

A mixture of 23.6 g of pyruvic aldehyde dimethylacetal and 23.8 g ofN,N-dimethylformamide dimethylacetal was stirred at 80° C. for 4 hourswhile produced methanol was distilled off, to obtain 38.8 g (purity:about 80%) of 4-dimethylamino-1,1-dimethoxy-3-butene-2-one of theformula:

4-Dimethylamino-1,1-dimethoxy-3-butene-2-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.87 (3H, s), 3.11 (3H, s), 3.41 (6H, s),4.58 (1H, s), 5.35 (1H, d, J=12 Hz), 7.74 (1H, d, J=12 Hz).

REFERENCE PREPARATION EXAMPLE 82-(2)

A mixture of 5 g of 4-dimethylamino-1,1-dimethoxy-3-butene-2-one, 1.7 mlof hydrazine monohydrate and 15 ml of methanol was stirred for 8 hoursunder heat refluxing. The reaction mixture was concentrated underreduced pressure to obtain 4.07 g of 3-(dimethoxymethyl)-1H-pyrazole ofthe formula:

3-(Dimethoxymethyl)-1H-pyrazole

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.37 (6H, s), 5.58 (1H, s), 6.35 (1H, d,J=2 Hz), 7.58 (1H, d, J=2 Hz).

REFERENCE PREPARATION EXAMPLE 82-(3)

According to the same manner as that of Reference Preparation Example22, 3-(dimethoxymethyl)-1H-pyrazole was used in place of3-bromo-1H-pyrazole to obtain3-chloro-2-[3-(dimethoxymethyl)-1H-pyrazol-1-yl]pyridine of the formula:

3-Chloro-2-[3-(dimethoxymethyl)-1H-pyrazol-1-yl]pyridine

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.44 (6H, s), 5.58 (1H, s), 6.57 (1H, d,J=2 Hz), 7.29 (1H, dd, J=8 Hz, 5 Hz), 7.90 (1H, dd, J=8 Hz, 2 Hz), 8.07(1H, d, 2 Hz), 8.47 (1H, dd, 5 Hz, 2 Hz).

REFERENCE PREPARATION EXAMPLE 82-(4)

A mixture of 3.35 g of3-chloro-2-[3-(dimethoxymethyl)-1H-pyrazol-1-yl]pyridine, 24 ml offormic acid and 6 ml of water was stirred at 60° C. for 1 hour. Thereaction mixture was concentrated under reduced pressure. Ice water waspoured into the residue, and a precipitated solid was collected byfiltration to obtain 2.38 g of1-(3-chloro-2-pyridinyl)-1H-pyrazole-3-carbaldehyde of the formula:

1-(3-Chloro-2-pyridinyl)-1H-pyrazole-3-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.01 (1H, d, J=2 Hz), 7.40 (1H, dd, J=8 Hz,5 Hz), 7.98 (1H, dd, J=8 Hz, 2 Hz), 8.18 (1H, dd, J=3 Hz, 2 Hz), 8.52(1H, dd, 5 Hz, 2 Hz), 10.14 (1H, d, 2 Hz).

REFERENCE PREPARATION EXAMPLE 82-(5)

A mixture of 2.00 g of1-(3-chloro-2-pyridinyl)-1H-pyrazole-3-carbaldehyde, 1.21 g ofO-methylhydroxylamine hydrochloride and 8 ml of pyridine was heated toreflux for 1 hour. After the reaction mixture was concentrated underreduced pressure, an aqueous saturated sodium hydrogen carbonatesolution was poured into the residue and the mixture was extracted withmethyl t-butyl ether three times. The organic layers were combined,washed successively with water and an aqueous saturated sodium chloridesolution, dried over anhydrous magnesium sulfate, and concentrated underreduced pressure to obtain 2.23 g of1-(3-chloro-2-pyridinyl)-1H-pyrazole-3-carbaldehyde O-methyloxime of theformula:

as a mixture of an E isomer and Z isomer (E isomer: Z isomer=3:1).

1-(3-Chloro-2-pyridinyl)-1H-pyrazole-3-carbaldehyde O-methyloxime

¹H-NMR (CDCl₃, TMS) δ (ppm):

E isomer: 3.99 (3H, s), 6.84 (1H, d, J=3 Hz), 7.30 (1H, dd, J=8 Hz, 5Hz), 7.92 (1H, dd, J=8 Hz, 2 Hz), 8.12 (1H, dd, J=3 Hz, 1Hz), 8.25 (1H,s), 8.48 (1H, dd, J=5 Hz, 2 Hz).

Z isomer: 4.07 (3H, s), 7.18 (1H, d, J=3 Hz), 7.33 (1H, dd, J=8 Hz, 5Hz), 7.67 (1H, s), 7.93 (1H, dd, J=8 Hz, 2 Hz), 8.14 (1H, dd, J=3 Hz,1Hz), 8.49 (1H, dd, J=5 Hz, 2 Hz).

REFERENCE PREPARATION EXAMPLE 82-(6)

According to the same manner as that of Reference Preparation Example23, 1-(3-chloro-2-pyridinyl)-1H-pyrazole-3-carbaldehyde O-methyloximewas used in place of 2-(3-bromo-1H-pyrazol-1-yl)-3-chloropyridine toobtain1-(3-chloro-2-pyridinyl)-3-methoxyiminomethyl-1H-pyrazole-5-carboxylicacid of the formula:

as a mixture of an E isomer and a Z isomer (E isomer: Z isomer=3:1).

1-(3-Chloro-2-pyridinyl)-3-methoxyiminomethyl-1H-pyrazole-5-carboxylicAcid

¹H-NMR (CDCl₃, TMS) δ (ppm):

E isomer: 4.00 (3H, s), 7.39 (1H, s), 7.45 (1H, dd, J=8 Hz, 5 Hz), 7.92(1H, dd, J=8 Hz, 2 Hz), 8.15 (1H, s), 8.51 (1H, dd, J=5 Hz, 2 Hz).

Z isomer: 4.08 (3H, s), 7.38 (1H, s), 7.51 (1H, dd, J=8 Hz, 5 Hz), 7.60(1H, s), 7.94 (1H, dd, J=8 Hz, 2 Hz), 8.51 (1H, dd, J=5 Hz, 2 Hz).

REFERENCE PREPARATION EXAMPLE 82-(7)

A mixture of 0.70 g of1-(3-chloro-2-pyridinyl)-3-methoxyiminomethyl-1H-pyrazole-5-carboxylicacid and 0.55 ml of thionyl chloride was heated to reflux for 1 hour.The reaction mixture was allowed to cool to room temperature, and thenconcentrated under reduced pressure. After the resulting residue wasdissolved in 10 ml of acetonitrile, 0.46 g of2-amino-5-chloro-3-methylbenzoic acid was added and the mixture wasstirred at room temperature for 10 minutes. To the mixture was added0.35 ml of triethylamine, and the mixture was stirred at roomtemperature for 20 minutes. Further 70 ml of triethylamine was added,and the mixture was stirred at room temperature for 20 minutes. Then0.21 ml of methanesulfonyl chloride was added, and the mixture wasstirred at room temperature for 17 hours. Water was added to thereaction mixture, and the mixture was extracted with chloroform threetimes. The organic layers were combined, washed with an aqueoussaturated sodium chloride solution, dried over anhydrous magnesiumsulfate, and concentrated under reduced pressure. The residue wassubjected to silica gel column chromatography to obtain 0.16 g of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-cyano-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[1-(3-chloro-2-pyridinyl)-3-cyano-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.83 (3H, s), 7.52 (1H, dd, J=2 Hz, 1Hz),7.56 (1H, dd, 8 Hz, 5 Hz), 7.58 (1H, s), 7.99-8.03 (2H, m), 8.58 (1H,dd, J=5 Hz, 2 Hz).

REFERENCE PREPARATION EXAMPLE 83

To a mixture of 10.6 ml of methylhydrazine, 50 ml of methanol and 8.0 gof sodium hydroxide was added dropwise 15.4 ml of methyl chloroformateunder ice-cooling, and the mixture was stirred at room temperature for 1hour. The reaction mixture was filtered, and the filtrate wasconcentrated. The residue was distilled under reduced pressure (50 to80° C./15 mmHg) to obtain 13.4 g of N-methyl-N-methoxycarbonylhydrazine.N-methyl-N-methoxycarbonylhydrazine

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.11 (3H, s), 3.73 (3H, s), 4.13 (2H, brs).

REFERENCE PREPARATION EXAMPLE 84

A mixture of 1.0 g of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one,0.35 ml of methylhydrazine and 20 ml of tetrahydrofuran was stirred atroom temperature for 24 hours. Water was poured into the reactionmixture and the mixture was extracted with ethyl acetate three times.The combined organic layer was washed with an aqueous saturated sodiumchloride solution, dried over anhydrous sodium sulfate, and concentratedunder reduced pressure. The residue was subjected to silica gel columnchromatography to obtain 0.85 g of3-bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideof the formula:

3-Bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.20 (3H, s), 3.21 (3H, s), 3.74 (3H, brs),7.05 (1H, s), 7.26-7.38 (3H, m), 7.86 (1H, dd, J=8 Hz, 2 Hz), 8.03 (1H,s), 8.42 (1H, dd, J=5 Hz, 2 Hz), 9.47 (1H, s).

REFERENCE PREPARATION EXAMPLE 85-(1)

To a mixture of 0.34 g of 2-amino-4-chloro-3-methylbenzoic acid and 10ml of N,N-dimethylformamide was added 0.26 g of N-chlorosuccinimide atroom temperature, and the mixture was stirred at room temperature for 5hours. After 30 ml of water was poured into the reaction mixture, themixture was extracted with ethyl acetate three times. The organic layerswere combined, dried over anhydrous sodium sulfate, and concentratedunder reduced pressure to obtain 0.22 g of2-amino-4,5-dichloro-3-methylbenzoic acid of the formula:

2-Amino-4,5-dichloro-3-methylbenzoic Acid

¹H-NMR (DMSO-d₆, TMS) δ: 2.25 (3H, s), 7.76 (1H, s).

REFERENCE PREPARATION EXAMPLE 85-(2)

According to the same manner as that of Reference Preparation Example46-(1), 2-amino-4,5-dichloro-3-methylbenzoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6,7-dichloro-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6,7-dichloro-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ: 1.82 (3H, s), 7.57 (1H, s), 7.77 (1H, dd, J=8Hz, 5 Hz), 8.14 (1H, s), 8.36 (1H, d, J=8 Hz), 8.64 (1H, d, J=5 Hz).

REFERENCE PREPARATION EXAMPLE 86-(1)

A mixture of 1.0 g of 2-amino-5-iodo-3-methylbenzoic acid, 0.45 g ofcopper cyanide and 10 ml of N,N-dimethylformamide was stirred at 150° C.for 9 hours. The reaction mixture was concentrated under reducedpressure. Into the residue, 20 ml of water and 2 ml of ethylenediaminewere poured, and the mixture was stirred at room temperature for 1 hour.After the reaction mixture was filtered, the filtrate was adjusted toaround pH 5 by an addition of concentrated hydrochloric acid, and thenextracted with ethyl acetate three times. The combined organic layer wasdried over sodium sulfate, and concentrated under reduced pressure toobtain 0.40 g of 2-amino-5-cyano-3-methylbenzoic acid of the formula:

2-Amino-5-cyano-3-methylbenzoic Acid

¹H-NMR (DMSO-d₆, TMS) δ: 2.13 (3H, s), 7.34 (2H, brs), 7.51 (1H, d, J=2Hz), 7.97 (1H, d, J=2 Hz).

REFERENCE PREPARATION EXAMPLE 86-(2)

According to the same manner as that of Reference Preparation Example46-(1), 2-amino-5-cyano-3-methylbenzoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-methyl-6-cyano-4H-3,1-benzoxazine-4-oneof the formula:

2-[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-methyl-6-cyano-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ: 1.73 (3H, s), 7.60 (1H, s), 7.77 (1H, dd, J=8Hz, 5 Hz), 8.10 (1H, d, J=2 Hz), 8.34-8.39 (2H, m), 8.63 (1H, d, J=5Hz).

REFERENCE PREPARATION EXAMPLE 87-(1)

To a mixture of 15.1 g of N-methyl anthranilic acid and 300 ml aceticacid was added dropwise 3.2 g of bromine over 15 minutes. The resultingmixture was stirred at room temperature for 5 hours. Further 1.6 g ofbromine was added dropwise thereto over 15 minutes, and the mixture wasstirred at room temperature for 3 hours. The reaction mixture wasfiltered, and the resulting solid was washed successively with aceticacid, ethyl acetate and acetone to obtain 23 g of3,5-dibromo-2-methylaminobenzoic acid of the formula:

3,5-Dibromo-2-methylaminobenzoic Acid

¹H-NMR (DMSO-d₆, TMS) δ: 2.89-2.92 (3H, m), 7.76-7.79 (1H, m), 7.83-7.86(1H, m).

REFERENCE PREPARATION EXAMPLE 87-(2)

A mixture of 1.0 g of3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid, 2 ml ofthionyl chloride and one drop of N,N-dimethylformamide was stirred at80° C. for 1 hour. After the reaction mixture was concentrated underreduced pressure, 10 ml of hexane was added and the mixture was furtherconcentrated under reduced pressure. The resulting residue was mixedwith 20 ml of acetonitrile and 0.93 g of3,5-dibromo-2-methylaminobenzoic acid. After the mixture was stirred atroom temperature for 1 hour, 0.6 g of triethylamine was added and themixture was further stirred at room temperature for 1 hour. The reactionmixture was poured into 30 ml of water, and the mixture was extractedwith ethyl acetate three times. The organic layers were combined, washedsuccessively with water and an aqueous saturated sodium chloridesolution, dried over anhydrous sodium sulfate, and concentrated underreduced pressure. The residue was washed with methyl t-butyl ether toobtain 1.3 g of3,5-dibromo-2-{N-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carbonyl]-N-methylamino}benzoicacid of the formula:

3,5-Dibromo-2-{N-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carbonyl]-N-methylamino}benzoicAcid

¹H-NMR (DMSO-d₆, TMS) δ: 2.98-3.34 (3H, m), 5.95 (1H, s), 7.62 (1H, dd,J=8 Hz, 5 Hz), 7.70 (1H, d, J=2 Hz), 7.89 (1H, d, J=2 Hz), 8.18 (1H, d,J=8 Hz), 8.49 (1H, d, J=5 Hz).

REFERENCE PREPARATION EXAMPLE 88

To a mixture of 0.13 g of N,N′-dimethylhydrazine dihydrochloride, 1 mlof water, 0.14 g of potassium carbonate and 10 ml of tetrahydrofuran wasadded 0.23 g of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one,and the resulting mixture was stirred at room temperature for 3 hours.The reaction mixture was poured into 30 ml of water, and the mixture wasextracted with ethyl acetate three times. The organic layers werecombined, dried over anhydrous sodium sulfate, and concentrated underreduced pressure. The residue was washed with ethyl acetate to obtain0.35 g of3-bromo-N-[4-chloro-2-(N,N′-dimethylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideof the formula:

3-Bromo-N-[4-chloro-2-(N,N′-dimethylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ: 1.99-2.40 (6H, m), 2.98-3.09 (3H, m), 4.61(0.7H, brs), 5.68 (0.3H, brs), 7.14-7.51 (3H, m), 7.61 (1H, dd, J=8 Hz,5 Hz), 8.18 (1H, d, J=5 Hz), 8.50 (1H, d, J=2 Hz), 10.03 (0.6H, brs),10.39 (0.4H, brs).

REFERENCE PREPARATION EXAMPLE 89-(1)

To a mixture of 0.78 g of 2-amino-5-fluorobenzoic acid and 100 ml ofN,N-dimethylformamide was added 1.1 g of N-bromosuccinimide at roomtemperature, and the mixture was stirred at room temperature for 5hours. After water was added to the reaction mixture, a depositedprecipitate was collected by filtration, and then washed with acetone toobtain 0.43 g of 2-amino-3-bromo-5-fluorobenzoic acid of the formula:

2-Amino-3-bromo-5-fluorobenzoic Acid

¹H-NMR (DMSO-d₆, TMS) δ: 7.55 (1H, dd, J=8 Hz, 3 Hz), 7.71 (1H, dd, J=8Hz, 3 Hz).

REFERENCE PREPARATION EXAMPLE 89-(2)

According to the same manner as that of Reference Preparation Example46-(1), 2-amino-3-bromo-5-fluorobenzoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-bromo-6-fluoro-4H-3,1-benzoxazine-4-oneof the formula:

2-[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-bromo-6-fluoro-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ: 7.54 (1H, s), 7.72 (1H, dd, J=8 Hz, 5 Hz), 7.92(1H, dd, J=8 Hz, 3 Hz), 8.15 (1H, dd, J=8 Hz, 3 Hz), 8.32 (1H, dd, J=8Hz, 1Hz), 8.59 (1H, dd, J=5 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 90-(1)

According to the same manner as that of Reference Preparation Example63-(1), 2-phenylaniline was used in place of 3-chloro-2-methylaniline toobtain N-(biphenyl-2-yl)-2-(hydroxyimino)acetamide of the formula:

N-(biphenyl-2-yl)-2-(hydroxyimino)acetamide

¹H-NMR (DMSO-d₆, TMS) δ: 7.27-7.48 (9H, m), 7.83 (1H, d, J=8 Hz), 9.18(1H, s), 12.14 (1H, s).

REFERENCE PREPARATION EXAMPLE 90-(2)

According to the same manner as that of Reference Preparation Example63-(2), N-(biphenyl-2-yl)-2-(hydroxyimino)acetamide was used in place ofN-(3-chloro-2-methylphenyl)-2-(hydroxyimino)acetamide to obtain7-phenyl-1H-indole-2,3-dione of the formula:

7-Phenyl-1H-indole-2,3-dione

¹H-NMR (DMSO-d₆, TMS) δ: 7.18 (1H, t, J=8 Hz), 7.40-7.63 (7H, m), 10.91(1H, s).

REFERENCE PREPARATION EXAMPLE 90-(3)

According to the same manner as that of Reference Preparation Example63-(3), 7-phenyl-1H-indole-2,3-dione was used in place of6-chloro-7-methyl-1H-indole-2,3-dione to obtain 2-amino-3-phenylbenzoicacid of the formula:

2-Amino-3-phenylbenzoic Acid

¹H-NMR (DMSO-d₆, TMS) δ: 6.65 (1H, t, J=8 Hz), 7.17 (1H, d, J=7 Hz),7.35-7.55 (5H, m), 7.78 (1H, d, J=8 Hz).

REFERENCE PREPARATION EXAMPLE 90-(4)

According to the same manner as that of Reference Preparation Example46-(1), 2-amino-3-phenylbenzoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-phenyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-phenyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ: 7.05-7.48 (7H, m), 7.61-7.89 (3H, m), 8.09-8.28(2H, m)

REFERENCE PREPARATION EXAMPLE 91

According to the same manner as that of Reference Preparation Example71-(5), 2-amino-3,5-dibromobenzoic acid was used in place of2-amino-5-chloro-3-methylbenzoic acid to obtain6,8-dibromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-oneof the formula:

6,8-Dibromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.11 (1H, d, J=2 Hz), 7.37 (1H, d, J=2 Hz),7.41 (1H, dd, J=8 Hz, 5 Hz), 7.92 (1H, dd, J=8 Hz, 2 Hz), 7.97 (1H, d,J=2 Hz), 8.20 (1H, d, J=2 Hz), 8.51 (1H, dd, J=5 Hz, 2 Hz).

REFERENCE PREPARATION EXAMPLE 92

According to the same manner as that of Reference Preparation Example71-(5), 2-amino-3-bromo-5-chlorobenzoic acid was used in place of2-amino-5-chloro-3-methylbenzoic acid to obtain8-bromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-4H-3,1-benzoxazine-4-oneof the formula:

8-Bromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.11 (1H, d, J=2 Hz), 7.37 (1H, d, J=2 Hz),7.41 (1H, dd, J=8 Hz, 5 Hz), 7.82 (1H, d, J=2 Hz), 7.92 (1H, dd, J=8 Hz,2 Hz), 8.05 (1H, d, J=2 Hz), 8.51 (1H, dd, J=5 Hz, 2 Hz).

REFERENCE PREPARATION EXAMPLE 93

According to the same manner as that of Reference Preparation Example71-(5), 2-amino-5-cyano-3-methylbenzoic acid was used in place of2-amino-5-chloro-3-methylbenzoic acid to obtain2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-cyano-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[4-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-cyano-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.68 (3H, s), 7.35 (1H, d, J=2 Hz), 7.67(1H, dd, J=8 Hz, 5 Hz), 7.70 (1H, d, J=2 Hz), 7.97 (1H, s), 8.23 (1H,dd, J=8 Hz, 2 Hz), 8.28 (1H, s), 8.57 (1H, dd, J=5 Hz, 2 Hz).

REFERENCE PREPARATION EXAMPLE 94-(1)

According to the same manner as that of Reference Preparation Example63-(1), 2-ethylaniline was used in place of 3-chloro-2-methylaniline toobtain N-(2-ethylphenyl)-2-(hydroxyimino)acetamide of the formula:

N-(2-ethylphenyl)-2-(hydroxyimino)acetamide

¹H-NMR (DMSO-d₆, TMS) δ:1.12 (3H, t, J=8 Hz), 2.59 (2H, q, J=8 Hz),7.15-7.27 (3H, m), 7.43 (1H, dd, J=6 Hz, 4 Hz), 7.67 (1H, s), 9.49 (1H,s), 12.17 (1H, s).

REFERENCE PREPARATION EXAMPLE 94-(2)

According to the same manner as that of Reference Preparation Example63-(2), N-(2-ethylphenyl)-2-(hydroxyimino)acetamide was used in place ofN-(3-chloro-2-methylphenyl)-2-(hydroxyimino)acetamide to obtain crude7-ethyl-1H-indole-2,3-dione of the formula:

REFERENCE PREPARATION EXAMPLE 94-(3)

A mixture of 1.0 g of crude 7-ethyl-1H-indole-2,3-dione and 3 ml of a 2Naqueous sodium hydroxide solution was added dropwise to 2 g of aqueoushydrogen peroxide (30%) at room temperature, and the resulting mixturewas stirred at room temperature for 1 hour. The reaction mixture wasadjusted to pH 4 by an addition of 2N hydrochloric acid, and a depositedprecipitate was collected by filtration. The resulting filter cake waspartitioned between ethyl acetate and a saturated sodium hydrogencarbonate solution. The aqueous layer was adjusted to pH 4 by anaddition of 2N hydrochloric acid, and a deposited precipitate wascollected by filtration to obtain 0.42 g of 2-amino-3-ethylbenzoic acidof the formula:

2-Amino-3-ethylbenzoic Acid

¹H-NMR (DMSO-d₆, TMS) δ: 1.15 (3H, t, J=7 Hz), 2.44-2.53 (2H, m), 6.50(1H, dd, J=8 Hz, 7 Hz), 7.15 (1H, d, J=7 Hz), 7.62 (1H, d, J=8 Hz).

REFERENCE PREPARATION EXAMPLE 94-(4)

According to the same manner as that of Reference Preparation Example46-(1), 2-amino-3-ethylbenzoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-ethyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-ethyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ: 0.81 (3H, t, J=7 Hz), 2.07 (2H, q, J=7 Hz),7.47-7.57 (2H, m), 7.70 (1H, d, J=7 Hz), 7.79 (1H, dd, J=8.5 Hz), 7.95(1H, d, J=7 Hz), 8.37 (1H, d, J=8 Hz), 8.64 (1H, d, J=5 Hz)

REFERENCE PREPARATION EXAMPLE 95-(1)

According to the same manner as that of Reference Preparation Example67-(1), cyclohexylhydrazine hydrochloride was used in place oftert-butylhydrazine hydrochloride to obtain1-cyclohexyl-3-trifluoromethyl-1H-pyrazole of the formula:

1-Cyclohexyl-3-trifluoromethyl-1H-pyrazole

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.19-1.33 (3H, m), 1.67-1.77 (2H, m),1.93-1.99 (4H, m), 2.16-2.19 (1H, m), 4.13-4.20 (1H, m), 6.49 (1H, s),7.45 (1H, s).

REFERENCE PREPARATION EXAMPLE 95-(2)

According to the same manner as that of Reference Preparation Example15, 1-cyclohexyl-3-trifluoromethyl-1H-pyrazole was used in place of3-chloro-2-(3-trifluoromethyl-1H-pyrazole-1-yl)pyridine to obtain1-cyclohexyl-3-trifluoromethyl-1H-pyrazole-5-carboxylic acid of theformula:

1-Cyclohexyl-3-trifluoromethyl-1H-pyrazole-5-carboxylic Acid

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.26-2.00 (10H, m), 5.10-5.18 (1H, m), 7.15(1H, s).

REFERENCE PREPARATION EXAMPLE 95-(3)

According to the same manner as that of Reference Preparation Example13, 1-cyclohexyl-3-trifluoromethyl-1H-pyrazole-5-carboxylic acid wasused in place of 1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acidto obtain6-chloro-2-(1-cyclohexyl-3-trifluoromethyl-1H-pyrazol-5-yl)-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-(1-cyclohexyl-3-trifluoromethyl-1H-pyrazol-5-yl)-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.26-1.54 (4H, m), 1.77 (1H, d, J=2 Hz),1.96-2.62 (5H, m), 2.62 (3H, s), 5.51-5.58 (1H, m), 7.31 (1H, s), 7.69(1H, d, J=2 Hz), 8.07 (1H, d, J=2 Hz).

REFERENCE PREPARATION EXAMPLE 95-(4)

According to the same manner as that of Reference Preparation Example 1,6-chloro-2-(1-cyclohexyl-3-trifluoromethyl-1H-pyrazol-5-yl)-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-cyclohexyl-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-cyclohexyl-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.20-1.39 (3H, m), 1.66 (1H, d, J=12 Hz),1.75-1.84 (4H, m), 1.98 (2H, d, J=10 Hz), 2.25 (3H, s), 4.36 (2H, brs),5.03-5.09 (1H, m), 7.35 (2H, s), 7.52 (1H, s), 9.62 (1H, brs), 10.17(1H, brs).

REFERENCE PREPARATION EXAMPLE 96-(1)

To a solution of 1.0 g of 3-chloro-2-(2-formyl-1H-pyrrol-1-yl)pyridinein 15 ml of N,N-dimethylformamide, 1.9 g of N-bromosuccinimide wasadded. The mixture was stirred at room temperature for 3 hours. Waterwas poured into the reaction mixture, and the mixture was extracted withethyl acetate three times. The organic layers were combined, washed withan aqueous saturated sodium chloride solution, dried over anhydrousmagnesium sulfate, and concentrated under reduced pressure to obtain 1.2g of 4,5-dibromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde ofthe formula:

4,5-Dibromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.14 (1H, s), 7.47 (1H, dd, J=8 Hz, 5 Hz),7.93 (1H, dd, J=8 Hz, 2 Hz), 8.53 (1H, dd, J=5 Hz, 2 Hz), 9.33 (1H, s).

REFERENCE PREPARATION EXAMPLE 96-(2)

To a mixture of 1.0 g of4,5-dibromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde, 15 ml ofacetone and 7 ml of water was slowly added 1.3 g of potassiumpermanganate at 40° C. The resulting mixture was stirred at 60° C. for 2hours. Precipitates in the reaction mixture were removed by filtration.The resulting filtrate was washed with chloroform two times. The aqueouslayer was adjusted to around pH 3 by an addition of 2N hydrochloric acidand then extracted with ethyl acetate three times. The organic layerswere combined, washed with an aqueous saturated sodium chloridesolution, dried over anhydrous magnesium sulfate, and then concentratedunder reduced pressure to obtain 0.69 g of4,5-dibromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid of theformula:

4,5-Dibromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.15 (1H, m), 7.64 (1H, dd, J=8 Hz, 5Hz), 8.19 (1H, dd, J=8 Hz, 2 Hz), 8.56 (1H, dd, J=5 Hz, 2 Hz).

REFERENCE PREPARATION EXAMPLE 96-(3)

According to the same manner as that of Reference Preparation Example71-(5), 4,5-dibromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylicacid was used in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid to obtain2-[4,5-dibromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[4,5-Dibromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.72 (3H, s), 7.40 (2H, s), 7.48 (1H, dd,J=8 Hz, 5 Hz), 7.92 (1H, s), 7.98 (1H, dd, J=8 Hz, 2 Hz), 8.58 (1H, dd,J=5 Hz, 2 Hz).

REFERENCE PREPARATION EXAMPLE 96-(4)

According to the same manner as that of Reference Preparation Example71-(6),2-[4,5-dibromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain4,5-dibromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

4,5-Dibromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.15 (3H, s), 4.03 (2H, brs), 7.15 (1H, s),7.22 (1H, d, J=3 Hz), 7.25 (1H, d, J=3 Hz), 7.37 (1H, dd, J=8 Hz, 5 Hz),7.70 (1H, brs), 7.86 (1H, dd, J=8 Hz, 2 Hz), 8.47 (1H, dd, J=5 Hz, 2Hz), 9.50 (1H, brs).

REFERENCE PREPARATION EXAMPLE 97-(1)

To a solution of 1.0 g of 3-chloro-2-(2-formyl-1H-pyrrol-1-yl)pyridinein 15 ml of N,N-dimethylformamide was added 0.68 g ofN-chlorosuccinimide. The resulting mixture was stirred at 50° C. for 2days. Water was poured into the reaction mixture, and the mixture wasextracted with ethyl acetate two times. The organic layers werecombined, washed successively with water and an aqueous saturated sodiumchloride solution, dried over anhydrous magnesium sulfate, andconcentrated under reduced pressure. The residue was subjected to silicagel column chromatography to obtain 0.35 g of4-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde of theformula:

and 0.31 g of5-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde of theformula:

4-Chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.04 (1H, d, J=2 Hz), 7.10 (1H, dd, J=2 Hz,1 Hz), 7.41 (1H, dd, J=8 Hz, 5 Hz), 7.89 (1H, dd, J=8 Hz, 2 Hz), 8.46(1H, dd, J=5 Hz, 2 Hz), 9.50 (1H, d, J=1 Hz)

5-Chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.41 (1H, d, J=4 Hz), 7.08 (1H, d, J=4 Hz),7.45 (1H, dd, J=8 Hz, 5 Hz), 7.92 (1H, dd, J=8 Hz, 2 Hz), 8.54 (1H, dd,J=5 Hz, 2 Hz), 9.41 (1H, s)

REFERENCE PREPARATION EXAMPLE 97-(2)

According to the same manner as that of Reference Preparation Example71-(4), 5-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde wasused in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde to obtain5-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid of theformula:

5-Chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 6.39 (1H, d, J=4 Hz), 7.01 (1H, d, J=4Hz), 7.62 (1H, dd, J=8 Hz, 5 Hz), 8.13 (1H, d, J=8 Hz), 8.54 (1H, d, J=5Hz)

REFERENCE PREPARATION EXAMPLE 97-(3)

According to the same manner as that of Reference Preparation Example71-(5), 5-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acidwas used in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid to obtain2-[5-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[5-Chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.71 (3H, s), 6.43 (1H, d, J=4 Hz), 7.32(1H, d, J=4 Hz), 7.38 (1H, d, J=2 Hz), 7.47 (1H, dd, J=8 Hz, 5 Hz), 7.92(1H, d, J=2 Hz), 7.97 (1H, dd, J=8 Hz, 2 Hz), 8.59 (1H, dd, J=5 Hz, 2Hz)

REFERENCE PREPARATION EXAMPLE 98-(1)

According to the same manner as that of Reference Preparation Example71-(4), 1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde was used inplace of 4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde toobtain 1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid of theformula:

1-(3-Chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS)_(b)(ppm): 6.33-6.34 (1H, m), 6.97 (1H, d, J=4 Hz),7.18 (1H, brs), 7.54 (1H, dd, J=8 Hz, 5 Hz), 8.10 (1H, d, J=8 Hz),8.47-8.49 (1H, m)

REFERENCE PREPARATION EXAMPLE 98-(2)

According to the same manner as that of Reference Preparation Example71-(5), 1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid was usedin place of 4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylicacid to obtain2-[1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[1-(3-Chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.73 (3H, s), 6.50 (1H, dd, J=4 Hz, 3 Hz),7.09 (1H, dd, J=3 Hz, 2 Hz), 7.36 (1H, dd, J=4 Hz, 2 Hz), 7.39 (1H, s),7.41 (1H, dd, J=8 Hz, 5 Hz), 7.90 (1H, dd, J=8 Hz, 2 Hz), 7.93 (1H, s),8.52 (1H, dd, J=5 Hz, 2 Hz)

REFERENCE PREPARATION EXAMPLE 98-(3)

According to the same manner as that of Reference Preparation Example71-(6),2-[1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.16 (3H, s), 4.40 (2H, brs), 6.37 (1H,dd, J=4 Hz, 3 Hz), 7.13-7.16 (2H, m), 7.31 (1H, d, J=2 Hz), 7.41 (1H,brs), 7.47 (1H, dd, J=8 Hz, 5 Hz), 8.02 (1H, d, J=8 Hz), 8.42 (1H, d,J=5 Hz), 9.56 (1H, brs), 9.84 (1H, brs)

REFERENCE PREPARATION EXAMPLE 99

According to the same manner as that of Reference Preparation Example 1,2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-cyano-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtain3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-(hydrazinocarbonyl)-6-methylphenyl]-1H-pyrazole-5-carboxamideof the formula:

3-Bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-(hydrazinocarbonyl)-6-methylphenyl]-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆) δ: 2.19 (3H, s), 4.41 (2H, brs), 7.41 (1H, s), 7.61(1H, dd, J=8 Hz, 5 Hz), 7.72 (1H, s), 7.88 (1H, s), 8.17 (1H, d, J=8Hz), 8.50 (1H, d, J=5 Hz), 9.65 (1H, brs), 10.52 (1H, brs)

REFERENCE PREPARATION EXAMPLE 100-(1)

To a solution of 3.0 g of 3-chloro-2-(2-formyl-1H-pyrrol-1-yl)pyridinein 10 ml of N,N-dimethylformamide was added 4.5 g ofN-chlorosuccinimide. The resulting mixture was stirred at 50° C. for 2hours. Water was poured into the reaction mixture, and the mixture wasextracted with ethyl acetate two times. The organic layers werecombined, washed successively with water and an aqueous saturated sodiumchloride solution, dried over anhydrous magnesium sulfate, andconcentrated under reduced pressure to obtain 3.6 g of4,5-dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde of theformula:

4,5-Dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.06 (1H, s), 7.47 (1H, dd, J=8 Hz, 5 Hz),7.93 (1H, dd, J=8 Hz, 2 Hz), 8.53 (1H, dd, J=5 Hz, 2 Hz), 9.37 (1H, s)

REFERENCE PREPARATION EXAMPLE 100-(2)

According to the same manner as that of Reference Preparation Example71-(4), 4,5-dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehydewas used in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde to obtain4,5-dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid ofthe formula:

4,5-Dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.18 (1H, s), 7.68 (1H, dd, J=8 Hz, 5Hz), 8.25 (1H, dd, J=8 Hz, 2 Hz), 8.59 (1H, dd, J=5 Hz, 2 Hz)

REFERENCE PREPARATION EXAMPLE 100-(3)

According to the same manner as that of Reference Preparation Example71-(5), 4,5-dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylicacid was used in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid to obtain2-[4,5-dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[4,5-Dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.71 (3H, s), 7.31 (1H, s), 7.40 (1H, s),7.49 (1H, dd, J=8 Hz, 5 Hz), 7.92 (1H, s), 7.98 (1H, d, J=8 Hz), 8.58(1H, d, J=5 Hz)

REFERENCE PREPARATION EXAMPLE 100-(4)

According to the same manner as that of Reference Preparation Example71-(6),2-[4,5-dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain4,5-dichloro-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

4,5-Dichloro-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.01 (3H, s), 4.03 (2H, brs), 7.07 (1H, s),7.16 (1H, d, J=2 Hz), 7.22 (1H, d, J=2 Hz), 7.37 (1H, dd, J=8 Hz, 5 Hz),7.47 (1H, brs), 7.86 (1H, dd, J=8 Hz, 2 Hz), 8.47 (1H, dd, J=5 Hz, 2Hz), 9.41 (1H, brs)

REFERENCE PREPARATION EXAMPLE 101

A mixture of 0.86 g of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one,0.11 g of methylhydrazine and 15 ml of tetrahydrofuran was stirred atroom temperature for 2 hours. Water was poured into the reactionmixture, and the mixture was extracted with ethyl acetate. The organiclayer was washed with water, dried over sodium sulfate, and concentratedunder reduced pressure. The resulting residue was subjected to silicagel chromatography to obtain 0.17 g of4-bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

4-Bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.14-2.16 (3H, m), 3.02-3.23 (3H, m), 4.04(0.7H, brs), 4.60 (1.3H, brs), 7.03 (2H, s), 7.11 (0.5H, s), 7.19 (0.5H,s), 7.31 (1H, dd, J=8 Hz, 4 Hz), 7.80 (1H, d, J=8 Hz), 8.41 (1H, d, J=4Hz), 8.56 (1H, brs)

REFERENCE PREPARATION EXAMPLE 102

According to the same manner as that of Reference Preparation Example46-(1), 2-amino-3,5-dichlorobenzoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6,8-dichloro-4H-3,1-benzoxazine-4-oneof the formula:

2-[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6,8-dichloro-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.57 (1H, s), 7.73 (1H, dd, J=8 Hz, 5Hz), 8.03 (1H, d, J=2 Hz), 8.12 (1H, d, J=2 Hz), 8.32 (1H, dd, J=8 Hz, 2Hz), 8.60 (1H, dd, J=5 Hz, 2 Hz).

REFERENCE PREPARATION EXAMPLE 103

According to the same manner as that of Reference Preparation Example84,2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-cyano-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1H-pyrazole-5-carboxamideof the formula:

3-Bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.22 (3H, s), 2.75-3.10 (3H, m),4.51-5.03 (2H, m), 7.36 (1H, s), 7.60-7.71 (2H, m), 7.74-7.88 (1H, m),8.20 (1H, d, J=8 Hz), 8.51 (1H, d, J=4 Hz), 10.27-10.63 (1H, m)

REFERENCE PREPARATION EXAMPLE 104

According to the same manner as that of Reference Preparation Example101,2-[4-bromo-1-(3-chloro-2-yridinyl)-1H-pyrrol-2-yl]-6-cyano-8-methyl-4H-3,1-enzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain4-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1H-pyrrole-2-carboxamideof the formula:

4-Bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1H-pyrrole-2-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.21 (3H, s), 2.74-3.10 (3H, m),4.51-4.99 (2H, m), 7.22-7.28 (1H, m), 7.46-7.56 (2H, m), 7.56-7.65 (1H,m), 7.70-7.84 (1H, m), 8.09 (1H, d, J=8 Hz), 8.44 (1H, d, J=4 Hz),9.76-10.04 (1H, m)

REFERENCE PREPARATION EXAMPLE 105-(1)

According to the same manner as that of Reference Preparation Example46-(1), 3-amino-4-bromo-2-naphthoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain10-bromo-2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-4H-naphtho[2,3-d][1,3]oxazine-4-oneof the formula:

10-Bromo-2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-4H-naphtho[2,3-d][1,3]oxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.55 (1H, s), 7.72-7.79 (2H, m), 7.89(1H, t, J=8 Hz), 8.23 (1H, d, J=8 Hz), 8.32 (1H, d, J=8 Hz), 8.37 (1H,dd, J=8 Hz, 1Hz), 8.63 (1H, dd, J=5 Hz, 1Hz), 8.93 (1H, s)

REFERENCE PREPARATION EXAMPLE 105-(2)

According to the same manner as that of Reference Preparation Example 1,10-bromo-2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-4H-naphtho[2,3-d][1,3]oxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtain3-bromo-N-[1-bromo-3-(hydrazinocarbonyl)-2-naphthyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideof the formula:

3-Bromo-N-[1-bromo-3-(hydrazinocarbonyl)-2-naphthyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 4.37 (2H, brs), 7.52 (1H, s), 7.59 (1H,dd, J=8 Hz, 4 Hz), 7.69 (1H, t, J=8 Hz), 7.77 (1H, t, J=8 Hz), 8.04-8.09(2H, m), 8.15 (1H, d, J=8 Hz), 8.21 (1H, d, J=8 Hz), 8.50 (1H, d, J=4Hz), 9.63 (1H, brs), 10.65 (1H, brs)

REFERENCE PREPARATION EXAMPLE 106-(1)

According to the same manner as that of Reference Preparation Example71-(5), 3-amino-4-bromo-2-naphthoic acid was used in place of2-amino-5-chloro-3-methylbenzoic acid to obtain10-bromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-naphtho[2,3-d][1,3]oxazine-4-oneof the formula:

10-Bromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-naphtho[2,3-d][1,3]oxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.33 (1H, d, J=2 Hz), 7.65-7.75 (3H, m),7.84 (1H, t, J=8 Hz), 8.17 (1H, d, J=8 Hz), 8.28 (2H, d, J=8 Hz),8.57-8.61 (1H, m), 8.87 (1H, s)

REFERENCE PREPARATION EXAMPLE 106-(2)

According to the same manner as that of Reference Preparation Example71-(6),10-bromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-naphtho[2,3-d][1,3]oxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain4-bromo-N-[1-bromo-3-(hydrazinocarbonyl)-2-naphthyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

4-Bromo-N-[1-bromo-3-(hydrazinocarbonyl)-2-naphthyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 4.37 (2H, brs), 7.40 (1H, s), 7.43-7.52(2H, m), 7.66 (1H, t, J=7 Hz), 7.75 (1H, t, J=7 Hz), 8.01-8.08 (3H, m),8.20 (1H, d, J=8 Hz), 8.43 (1H, d, J=5 Hz), 9.55 (1H, brs), 10.12 (1H,brs)

REFERENCE PREPARATION EXAMPLE 107

According to the same manner as that of Reference Preparation Example71-(6),2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-cyano-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain4-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-(hydrazinocarbonyl)-6-methylphenyl]-1H-pyrrole-2-carboxamideof the formula:

4-Bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-(hydrazinocarbonyl)-6-methylphenyl]-1H-pyrrole-2-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.18 (3H, s), 4.42 (2H, brs), 7.28 (1H,s), 7.45-7.55 (2H, m), 7.71 (1H, s), 7.84 (1H, s), 8.07 (1H, d, J=8 Hz),8.44 (1H, d, J=4 Hz), 9.68 (1H, brs), 10.16 (1H, brs)

REFERENCE PREPARATION EXAMPLE 108

According to the same manner as that of Reference Preparation Example88,2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-cyano-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-(N,N′-dimethylhydrazinocarbonyl)-6-methylphenyl]-1H-pyrazole-5-carboxamideof the formula:

3-Bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-(N,N′-dimethylhydrazinocarbonyl)-6-methylphenyl]-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.14-2.33 (6H, m), 2.70-3.09 (3H, m),4.55-6.05 (1H, m), 7.37 (1H, s), 7.58-7.66 (2H, m), 7.71-7.90 (1H, m),8.15-8.21 (1H, m), 8.48-8.52 (1H, m), 10.25-10.62 (1H, m)

REFERENCE PREPARATION EXAMPLE 109

To a mixture of 0.29 g of N,N′-dimethylhydrazine dihydrochloride, 1 mlof water, 0.31 g of potassium carbonate and 10 ml ofN,N-dimethylformamide was added 1.0 g of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one.The resulting mixture was stirred at room temperature for 6 hours. Waterwas poured into the reaction mixture, and the mixture was extracted withethyl acetate three times. The organic layers were combined, dried overanhydrous sodium sulfate, and concentrated under reduced pressure. Theresulting residue was subjected to silica gel chromatography to obtain0.26 g of4-bromo-N-[4-chloro-2-(N,N′-dimethylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

4-Bromo-N-[4-chloro-2-(N,N′-dimethylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.16 (3H, s), 2.43 (1H, d, J=6 Hz), 2.61(2H, d, J=6 Hz), 2.95 (2H, s), 3.19 (1H, s), 3.54 (0.3H, d, J=6 Hz),5.62 (0.7H, d, J=6 Hz), 7.01-7.07 (3H, m), 7.14-7.18 (1H, m), 7.30 (1H,dd, J=8 Hz, 5 Hz), 7.79 (1H, d, J=8 Hz), 8.40 (1H, d, J=5 Hz), 8.56 (1H,brs)

REFERENCE PREPARATION EXAMPLE 110-(1)

According to the same manner as that of Reference Preparation Example71-(5), 4,5-dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylicacid and 2-amino-3,5-dibromobenzoic acid were used in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid and2-amino-5-chloro-3-methylbenzoic acid respectively to obtain6,8-dibromo-2-[4,5-dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-oneof the formula:

6,8-Dibromo-2-[4,5-dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.36 (1H, s), 7.47 (1H, dd, J=8 Hz, 5 Hz),7.95 (1H, d, J=2 Hz), 7.99 (1H, dd, J=8 Hz, 2 Hz), 8.19 (1H, d, J=2 Hz),8.57 (1H, dd, J=5 Hz, 2 Hz)

REFERENCE PREPARATION EXAMPLE 110-(2)

According to the same manner as that of Reference Preparation Example71-(6),6,8-dibromo-2-[4,5-dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4,6-dibromo-2-(hydrazinocarbonyl)phenyl]-4,5-dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

N-[4,6-dibromo-2-(hydrazinocarbonyl)phenyl]-4,5-dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 4.40 (2H, brs), 6.47 (1H, s), 7.65 (1H,s), 7.75-7.76 (1H, m), 7.89 (1H, s), 8.05-8.06 (1H, m), 8.27-8.28 (1H,m), 9.64 (1H, brs), 10.20 (1H, brs)

REFERENCE PREPARATION EXAMPLE 111

According to the same manner as that of Reference Preparation Example46-(1), 3-amino-4-chloro-2-naphthoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-10-chloro-4H-naphtho[2,3-d][1,3]oxazine-4-oneof the formula:

2-[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-10-chloro-4H-naphtho[2,3-d][1,3]oxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.56 (1H, s), 7.73-7.81 (2H, m), 7.89(1H, t, J=8 Hz), 8.23 (1H, d, J=8 Hz), 8.34 (1H, d, J=8 Hz), 8.37 (1H,dd, J=8 Hz, 1Hz), 8.64 (1H, dd, J=5 Hz, 1Hz), 8.89 (1H, s)

REFERENCE PREPARATION EXAMPLE 112

According to the same manner as that of Reference Preparation Example71-(5), 3-amino-4-chloro-2-naphthoic acid was used in place of2-amino-5-chloro-3-methylbenzoic acid to obtain2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-10-chloro-4H-naphtho[2,3-d][1,3]oxazine-4-oneof the formula:

2-[4-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-10-chloro-4H-naphtho[2,3-d][1,3]oxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.33 (1H, d, J=2 Hz), 7.67-7.73 (2H, m),7.74 (1H, d, J=2 Hz), 7.82-7.87 (1H, m), 8.17 (1H, d, J=8 Hz), 8.26-8.31(2H, m), 8.59 (1H, dd, J=5 Hz, 1Hz), 8.84 (1H, s)

REFERENCE PREPARATION EXAMPLE 113-(1)

According to the same manner as that of Reference Preparation Example71-(4), 4-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide wasused in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde to obtain4-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid of theformula:

4-Chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 6.97 (1H, d, J=2 Hz), 7.48 (1H, d, J=2Hz), 7.59 (1H, dd, J=8 Hz, 5 Hz), 8.16 (1H, dd, J=8 Hz, 2 Hz), 8.50 (1H,dd, J=5 Hz, 2 Hz)

REFERENCE PREPARATION EXAMPLE 113-(2)

According to the same manner as that of Reference Preparation Example71-(5), 4-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acidwas used in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid to obtain2-[4-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[4-Chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.73 (3H, s), 7.03 (1H, d, J=2 Hz), 7.26(1H, d, J=2 Hz), 7.41 (1H, d, J=2 Hz), 7.43 (1H, dd, J=8 Hz, 5 Hz), 7.91(1H, dd, J=8 Hz, 2 Hz), 7.94 (1H, d, J=2 Hz), 8.51 (1H, dd, J=5 Hz, 2Hz)

REFERENCE PREPARATION EXAMPLE 113-(3)

According to the same manner as that of Reference Preparation Example71-(6),2-[4-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain4-chloro-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

4-Chloro-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.19 (3H, s), 6.97 (1H, d, J=2 Hz), 7.00(1H, d, J=2 Hz), 7.26 (1H, s), 7.30 (1H, dd, J=8 Hz, 5 Hz), 7.48 (1H,s), 7.79 (1H, dd, J=8 Hz, 2 Hz), 8.40 (1H, dd, J=5 Hz, 2 Hz), 9.29 (1H,brs)

REFERENCE PREPARATION EXAMPLE 114

According to the same manner as that of Reference Preparation Example84,2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6,8-dichloro-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain3-bromo-N-[4,6-dichloro-2-(N-methylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideof the formula:

3-Bromo-N-[4,6-dichloro-2-(N-methylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.76 (0.6H, s), 3.06 (2.4H, s), 4.55(1.6H, s), 5.02 (0.4H, s), 7.38-7.46 (2.0H, m), 7.60-7.64 (1.0H, m),7.71 (0.8H, d, J=2 Hz), 7.83 (0.2H, d, J=2 Hz), 8.17-8.20 (1.0H, m),8.51 (1.0H, dd, J=5 Hz, 2 Hz), 10.38 (0.8H, s), 10.64 (0.2H, s).

REFERENCE PREPARATION EXAMPLE 115-(1)

To a solution of 3.0 g of 3-chloro-2-(1H-pyrrol-1-yl)pyridine in 30 mlof N,N-dimethylformamide was added 3.1 g of N-bromosuccinimide. Theresulting mixture was stirred at room temperature for 6 hours. Water waspoured into the reaction mixture, and the mixture was extracted withethyl acetate two times. The organic layers were combined, washed withan aqueous saturated sodium chloride solution, dried over anhydrousmagnesium sulfate, and concentrated under reduced pressure. The residuewas subjected to silica gel column chromatography to obtain 1.1 g of2-(2-bromo-1H-pyrrol-1-yl)-3-chloropyridine of the formula:

2-(2-Bromo-1H-pyrrol-1-yl)-3-chloropyridine

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.37-6.41 (2H, m), 6.93 (1H, dd, J=3 Hz, 2Hz), 7.38 (1H, dd, J=8 Hz, 5 Hz), 7.91 (1H, dd, J=8 Hz, 2 Hz), 8.52 (1H,dd, J=5 Hz, 2 Hz)

REFERENCE PREPARATION EXAMPLE 115-(2)

According to the same manner as that of Reference Preparation Example71-(2), 2-(2-bromo-1H-pyrrol-1-yl)-3-chloropyridine was used in place of3-chloro-2-(1H-pyrrol-1-yl)pyridine to obtain5-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde of theformula:

5-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.53 (1H, d, J=4 Hz), 7.07 (1H, d, J=4 Hz),7.45 (1H, dd, J=8 Hz, 5 Hz), 7.92 (1H, dd, J=8 Hz, 2 Hz), 8.54 (1H, dd,J=5 Hz, 2 Hz), 9.36 (1H, s)

REFERENCE PREPARATION EXAMPLE 115-(3)

According to the same manner as that of Reference Preparation Example71-(4), 5-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde wasused in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde to obtain5-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid of theformula:

5-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 6.54 (1H, d, J=4 Hz), 7.02 (1H, d, J=4Hz), 7.63 (1H, dd, J=8 Hz, 5 Hz), 8.21 (1H, d, J=8 Hz), 8.56 (1H, d, J=5Hz), 12.54 (1H, brs)

REFERENCE PREPARATION EXAMPLE 115-(4)

According to the same manner as that of Reference Preparation Example71-(5), 5-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acidwas used in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid to obtain2-[5-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[5-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.57 (3H, s), 6.55 (1H, d, J=4 Hz), 7.33(1H, d, J=4 Hz), 7.38 (1H, d, J=2 Hz), 7.47 (1H, dd, J=8 Hz, 5 Hz), 7.92(1H, d, J=2 Hz), 7.97 (1H, dd, J=8 Hz, 2 Hz), 8.59 (1H, dd, J=5 Hz, 2Hz)

REFERENCE PREPARATION EXAMPLE 115-(5)

According to the same manner as that of Reference Preparation Example71-(6),2-[5-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain5-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

5-Bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.17 (3H, s), 4.02 (2H, brs), 6.47 (1H, d,J=4 Hz), 7.03 (1H, d, J=4 Hz), 7.20 (1H, s), 7.27 (1H, s), 7.36 (1H, dd,J=8 Hz, 5 Hz), 7.86 (1H, dd, J=8 Hz, 2 Hz), 8.40 (1H, dd, J=5 Hz, 2 Hz),9.22 (1H, brs)

REFERENCE PREPARATION EXAMPLE 116-(1)

A mixture of 1.9 g of 2-pyrrolecarbaldehyde, 2.3 g of2-chloropyrimidine, 7.8 g of cesium carbonate and 20 ml ofN-methylpyrrolidone was stirred at 130° C. for 13 hours, and thenallowed to cool to room temperature. Water was poured into the reactionmixture, and the mixture was extracted with ethyl acetate two times. Theorganic layers were combined, washed successively with water and anaqueous saturated sodium chloride solution, dried over anhydrous sodiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel chromatography to obtain 0.94 g of1-(2-pyrimidinyl)-1H-pyrrole-2-carbaldehyde of the formula:

1-(2-Pyrimidinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.40-6.41 (1H, m), 7.22 (1H, t, J=5 Hz),7.29 (1H, dd, J=4 Hz, 2 Hz), 7.96 (1H, dd, J=3 Hz, 2 Hz), 8.73 (2H, d,J=5 Hz), 10.61 (1H, s)

REFERENCE PREPARATION EXAMPLE 116-(2)

To a solution of 0.5 g of 1-(2-pyrimidinyl)-1H-pyrrole-2-carbaldehyde in10 ml of N,N-dimethylformamide was added 0.6 g of N-bromosuccinimide.The resulting mixture was stirred at room temperature for 1 hour. Waterwas poured into the reaction mixture, and the mixture was extracted withethyl acetate two times. The organic layers were combined, washedsuccessively with water and an aqueous saturated sodium chloridesolution, dried over anhydrous sodium sulfate, and concentrated underreduced pressure. The resulting residue was subjected to silica gelchromatography to obtain 0.43 g of5-bromo-1-(2-pyrimidinyl)-1H-pyrrole-2-carbaldehyde of the formula:

5-Bromo-1-(2-pyrimidinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 6.67 (1H, d, J=4 Hz), 7.28 (1H, d, J=4Hz), 7.75 (1H, t, J=5 Hz), 9.02 (2H, d, J=5 Hz), 9.39 (1H, s)

REFERENCE PREPARATION EXAMPLE 116-(3)

A solution of 2.0 g of potassium permanganate in 10 ml of water wasadded dropwise to a mixture of 0.76 g of5-bromo-1-(2-pyrimidinyl)-1H-pyrrole-2-carbaldehyde and 18 ml of acetonewhile the mixture was maintained at 40° C. The resulting mixture wasstirred at 40° C. for 4 hours. A precipitate was filtered off to obtaina filtrate. The filtrate was adjusted to pH 10-12 by an addition of a 2Naqueous sodium hydroxide solution, and then washed with chloroform twotimes. The aqueous layer was adjusted to around pH 3 by an addition of2N hydrochloric acid, and then extracted with ethyl acetate two times.The organic layers were combined, washed successively with water and anaqueous saturated sodium chloride solution, dried over anhydrous sodiumsulfate, and concentrated under reduced pressure to obtain 0.28 g of5-bromo-1-(2-pyrimidinyl)-1H-pyrrole-2-carboxylic acid of the formula:

5-Bromo-1-(2-pyrimidinyl)-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) (ppm): 6.40-6.51 (1H, m), 6.89-7.16 (1H, m),7.66-7.75 (1H, m), 8.99 (2H, d, J=5 Hz)

REFERENCE PREPARATION EXAMPLE 116-(4)

According to the same manner as that of Reference Preparation Example71-(5), 5-bromo-1-(2-pyrimidinyl)-1H-pyrrole-2-carboxylic acid was usedin place of 4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylicacid to obtain2-[5-bromo-1-(2-pyrimidinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[5-Bromo-1-(2-pyrimidinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.67 (3H, s), 6.62 (1H, d, J=4 Hz),7.20-7.30 (1H, m), 7.67-7.72 (1H, m), 7.77-7.88 (2H, m), 9.06-9.12 (2H,m)

REFERENCE PREPARATION EXAMPLE 116-(5)

According to the same manner as that of Reference Preparation Example71-(6),2-[5-bromo-1-(2-pyrimidinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain5-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-pyrimidinyl)-1H-pyrrole-2-carboxamideof the formula:

5-Bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-pyrimidinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.13 (3H, s), 6.45 (1H, d, J=4 Hz), 7.12(1H, brs), 7.30 (1H, brs), 7.44 (1H, brs), 7.59-7.66 (1H, m), 8.90-8.95(2H, m), 9.51 (1H, brs), 9.92 (1H, brs)

REFERENCE PREPARATION EXAMPLE 117-(1)

A mixture of 5 g of 2,6-dichloroaniline, 4.5 g of2,5-dimethoxytetrahydrofuran and 30 ml of acetic acid was heated toreflux for 10 hours. The reaction mixture was allowed to cool, pouredinto water, and extracted with ethyl acetate two times. The organiclayers were combined, washed successively with water and an aqueoussaturated sodium chloride solution, dried over anhydrous sodium sulfate,and concentrated under reduced pressure. The resulting residue wassubjected to silica gel chromatography to obtain 5.45 g of1-(2,6-dichlorophenyl)-1H-pyrrole of the formula:

1-(2,6-Dichlorophenyl)-1H-pyrrole

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 6.26 (2H, t, J=2 Hz), 6.82 (2H, t, J=2Hz), 7.50 (1H, t, J=8 Hz), 7.66 (2H, d, J=8 Hz)

REFERENCE PREPARATION EXAMPLE 117-(2)

Under ice-cooling, 7.67 g of phosphorus oxychloride was added dropwiseto 4 g of N,N-dimethylformamide. The mixture was stirred at roomtemperature for 30 minutes, and 2.1 g of1-(2,6-dichlorophenyl)-1H-pyrrole was added thereto. The resultingmixture was stirred at 60° C. for 2 hours, allowed to cool to roomtemperature, and then poured into ice water. The mixture was adjusted topH 4 by an addition of a 2N aqueous sodium hydroxide solution, and thenextracted with ethyl acetate two times. The organic layers werecombined, washed successively with water and an aqueous saturated sodiumchloride solution, dried over anhydrous sodium sulfate, and concentratedunder reduced pressure. The resulting residue was subjected to silicagel chromatography to obtain 0.80 g of1-(2,6-dichlorophenyl)-1H-pyrrole-2-carbaldehyde of the formula:

and 1.00 g of 1-(2,6-dichlorophenyl)-1H-pyrrole-3-carbaldehyde of theformula:

1-(2,6-Dichlorophenyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 6.54 (1H, dd, J=4 Hz, 3 Hz), 7.29 (1H,dd, J=4 Hz, 2 Hz), 7.35 (1H, ddd, J=3 Hz, 2 Hz, 1Hz), 7.53 (1H, dd, J=9Hz, 7 Hz), 7.63-7.67 (2H, m), 9.50 (1H, d, J=1 Hz)

1-(2,6-Dichlorophenyl)-1H-pyrrole-3-carbaldehyde

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 6.69 (1H, dd, J=3, 2 Hz), 7.07 (1H, ddd,J=3 Hz, 2 Hz, 1Hz), 7.58 (1H, dd, J=9 Hz, 8 Hz), 7.71-7.75 (2H, m), 7.85(1H, brs), 9.78 (1H, d, J=1 Hz)

REFERENCE PREPARATION EXAMPLE 117-(3)

In 10 ml of N,N-dimethylformamide was dissolved 0.65 g of1-(2,6-dichlorophenyl)-1H-pyrrole-2-carbaldehyde, and then 0.53 g ofN-bromosuccinimide was added thereto. The mixture was stirred at roomtemperature for 1 hour. Water was poured into the reaction mixture, adeposited precipitate was collected by filtration to obtain 0.85 g of4-bromo-1-(2,6-dichlorophenyl)-1H-pyrrole-2-carbaldehyde of the formula:

4-Bromo-1-(2,6-dichlorophenyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.43 (1H, d, J=2 Hz), 7.56 (1H, dd, J=9Hz, 7 Hz), 7.65-7.69 (3H, m), 9.46 (1H, s)

REFERENCE PREPARATION EXAMPLE 117-(4)

A solution of 2.0 g of potassium permanganate in 10 ml of water wasadded dropwise to a mixture of 0.85 g of4-bromo-1-(2,6-dichlorophenyl)-1H-pyrrole-2-carbaldehyde and 18 ml ofacetone while the mixture was maintained at 40° C. The resulting mixturewas stirred at 40° C. for 2 hours. A precipitate was filtered off toobtain a filtrate. The filtrate was adjusted to pH 10-12 by an additionof a 2N aqueous sodium hydroxide solution, and then extracted withchloroform two times. The aqueous layer was adjusted to around pH 3 byan addition of 2N hydrochloric acid, and then extracted with ethylacetate two times. The organic layers were combined, washed successivelywith water and an aqueous saturated sodium chloride solution, dried overanhydrous sodium sulfate, and concentrated under reduced pressure toobtain 0.66 g of 4-bromo-1-(2,6-dichlorophenyl)-1H-pyrrole-2-carboxylicacid of the formula:

4-Bromo-1-(2,6-dichlorophenyl)-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.05 (1H, brs), 7.40 (1H, brs), 7.51 (1H,t, J=8 Hz), 7.60-7.67 (2H, m), 12.65 (1H, s)

REFERENCE PREPARATION EXAMPLE 117-(5)

According to the same manner as that of Reference Preparation Example71-(5), 4-bromo-1-(2,6-dichlorophenyl)-1H-pyrrole-2-carboxylic acid wasused in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid to obtain2-[4-bromo-1-(2,6-dichlorophenyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[4-Bromo-1-(2,6-dichlorophenyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.68 (3H, s), 7.32 (1H, d, J=1 Hz),7.54-7.64 (2H, m), 7.67-7.77 (3H, m), 7.83 (1H, d, J=2 Hz)

REFERENCE PREPARATION EXAMPLE 117-(6)

According to the same manner as that of Reference Preparation Example71-(6),2-[4-bromo-1-(2,6-dichlorophenyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2,6-dichlorophenyl)-1H-pyrrole-2-carboxamideof the formula:

4-Bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2,6-dichlorophenyl)-1H-pyrrole-2-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.11 (3H, s), 4.38 (2H, brs), 7.27-7.30(2H, m), 7.34 (1H, d, J=2 Hz), 7.40-7.46 (2H, m), 7.56 (2H, d, J=8 Hz),9.51 (1H, brs), 9.81 (1H, brs)

REFERENCE PREPARATION EXAMPLE 118-(1)

A mixture of 2.6 g of 2-pyrrolecabaldehyde, 5.0 g of3,4,5-trichloropyridine, 10.7 g of cesium carbonate and 30 ml ofN-methylpyrrolidone was stirred at 100° C. for 2 hours, and then allowedto cool to room temperature. Water was poured into the reaction mixture,and the mixture was extracted with ethyl acetate two times. The organiclayers were combined, washed successively water and an aqueous saturatedsodium chloride solution, dried over anhydrous sodium sulfate, andconcentrated under reduced pressure. The resulting residue was subjectedto silica gel chromatography to obtain 2.14 g of1-(3,5-dichloro-4-pyridinyl)-1H-pyrrole-2-carbaldehyde of the formula:

1-(3,5-Dichloro-4-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 6.61 (1H, dd, J=4 Hz, 3 Hz), 7.37 (1H,dd, J=4 Hz, 2 Hz), 7.46 (1H, ddd, J=3 Hz, 2 Hz, 1Hz), 8.85 (2H, s), 9.54(1H, d, J=1 Hz)

REFERENCE PREPARATION EXAMPLE 118-(2)

To a solution of 2.14 g of1-(3,5-dichloro-4-pyridinyl)-1H-pyrrole-2-carbaldehyde in 10 ml ofN,N-dimethylformamide was added 1.7 g of N-bromosuccinimide. The mixturewas stirred at room temperature for 2 hours. Water was poured into thereaction mixture, and a deposited precipitate was collected byfiltration to obtain 2.9 g of4-bromo-1-(3,5-dichloro-4-pyridinyl)-1H-pyrrole-2-carbaldehyde of theformula:

4-Bromo-1-(3,5-dichloro-4-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.52 (1H, d, J=2 Hz), 7.74 (1H, dd, J=2Hz, 1Hz), 8.88 (2H, s), 9.51 (1H, d, J=1 Hz)

REFERENCE PREPARATION EXAMPLE 118-(3)

A solution of 2.9 g of potassium permanganate in 15 ml of water wasadded dropwise to a mixture of 2.86 g of4-bromo-1-(3,5-dichloro-4-pyridinyl)-1H-pyrrole-2-carbaldehyde and 30 mlof acetone while the mixture was maintained at 40° C. The mixture wasstirred at 40° C. for 2 hours. A precipitate was filtered off to obtaina filtrate. The filtrate was adjusted to pH 10-12 by an addition of a 2Naqueous sodium hydroxide solution, and then washed with chloroform twotimes. The aqueous layer was adjusted to around pH 3 by an addition of2N hydrochloric acid. A deposited precipitate was collected byfiltration to obtain 2.08 g of4-bromo-1-(3,5-dichloro-4-pyridinyl)-1H-pyrrole-2-carboxylic acid of theformula:

4-Bromo-1-(3,5-dichloro-4-pyridinyl)-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.12 (1H, d, J=2 Hz), 7.51 (1H, d, J=2Hz), 8.85 (2H, s)

REFERENCE PREPARATION EXAMPLE 118-(4)

According to the same manner as that of Reference Preparation Example71-(5), 4-bromo-1-(3,5-dichloro-4-pyridinyl)-1H-pyrrole-2-carboxylicacid was used in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid to obtain2-[4-bromo-1-(3,5-dichloro-4-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[4-Bromo-1-(3,5-dichloro-4-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.64 (3H, s), 7.39 (1H, brs), 7.72 (2H,s), 7.85 (1H, brs), 8.95 (2H, s)

REFERENCE PREPARATION EXAMPLE 118-(5)

According to the same manner as that of Reference Preparation Example71-(6),2-[4-bromo-1-(3,5-dichloro-4-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3,5-dichloro-4-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

4-Bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3,5-dichloro-4-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.13 (3H, s), 4.35 (2H, brs), 7.28 (1H,d, J=2 Hz), 7.37 (1H, d, J=2 Hz), 7.43-7.47 (2H, m), 8.76 (2H, s), 9.52(1H, brs), 9.89 (1H, brs)

REFERENCE PREPARATION EXAMPLE 119-(1)

A solution of 0.9 g of potassium permanganate in 10 ml of water wasadded dropwise to a mixture of 0.58 g of1-(2,6-dichlorophenyl)-1H-pyrrole-3-carbaldehyde and 20 ml of acetonewhile the mixture was maintained at 40° C. The resulting mixture wasstirred at 40° C. for 2 hours. A deposited precipitate was filtered offto obtain a filtrate. The filtrate was adjusted to pH 10-12 by anaddition of a 2N aqueous sodium hydroxide solution, and then washed withchloroform two times. The aqueous layer was adjusted to around pH 3 byan addition of 2N hydrochloric acid, and then extracted with ethylacetate two times. The organic layers were combined, washed successivelywith water and an aqueous saturated sodium chloride solution, dried overanhydrous sodium sulfate, and concentrated under reduced pressure toobtain 0.34 g of 1-(2,6-dichlorophenyl)-1H-pyrrole-3-carboxylic acid ofthe formula:

1-(2,6-Dichlorophenyl)-1H-pyrrole-3-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 6.60 (1H, dd, J=3 Hz, 2 Hz), 6.92 (1H,dd, J=3 Hz, 1Hz), 7.48 (1H, dd, J=2 Hz, 1Hz), 7.55 (1H, dd, J=8 Hz, 7Hz), 7.67-7.72 (2H, m), 12.05 (1H, brs)

REFERENCE PREPARATION EXAMPLE 119-(2)

According to the same manner as that of Reference Preparation Example71-(5), 1-(2,6-dichlorophenyl)-1H-pyrrole-3-carboxylic acid was used inplace of 4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acidto obtain6-chloro-2-[1-(2,6-dichlorophenyl)-1H-pyrrol-3-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[1-(2,6-dichlorophenyl)-1H-pyrrol-3-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.53 (3H, s), 6.89 (1H, s), 7.10 (1H, s),7.43-7.64 (2H, m), 7.67-7.77 (2H, m), 7.82-7.91 (2H, m)

REFERENCE PREPARATION EXAMPLE 119-(3)

According to the same manner as that of Reference Preparation Example71-(6),6-chloro-2-[1-(2,6-dichlorophenyl)-1H-pyrrol-3-yl]-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2,6-dichlorophenyl)-1H-pyrrole-3-carboxamideof the formula:

N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2,6-dichlorophenyl)-1H-pyrrole-3-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.22 (3H, s), 4.59 (2H, brs), 6.79 (1H,brs), 6.97 (1H, brs), 7.37 (1H, brs), 7.47-7.59 (3H, m), 7.71 (2H, d,J=8 Hz), 9.66 (1H, brs), 9.70 (1H, brs)

REFERENCE PREPARATION EXAMPLE 120

To a mixture of 4.61 g of methylhydrazine, 25 ml of methanol and 4.0 gof sodium hydroxide was added dropwise 10.8 g of N,N-dimethylcarbamoylchloride under ice-cooling. The mixture was stirred at room temperaturefor 1 hour. The reaction mixture was filtered, and the filtrate wasconcentrated under reduced pressure. The residue was distilled underreduced pressure (90 to 99° C./22 mmHg) to obtain 5.70 g of2,4,4-trimethylsemicarbazide of the formula:

2,4,4-Trimethylsemicarbazide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.90 (6H, s), 2.95 (3H, s), 3.94 (2H, brs).

REFERENCE PREPARATION EXAMPLE 121

According to the same manner as that of Reference Preparation Example101,2-[4,5-dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain4,5-dichloro-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

4,5-Dichloro-N-[4-chloro-2-(N-methylhydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.01-2.05 (3H, m), 2.92 (2H, s), 3.21 (1H,s), 4.05 (0.7H, brs), 4.59 (1.3H, brs), 6.95-7.10 (2H, m), 7.19 (0.6H,s), 7.29 (0.4H, s), 7.37 (1H, dd, J=8 Hz, 4 Hz), 7.86 (1H, d, J=8 Hz),8.48 (1H, d, J=5 Hz), 9.11 (0.6H, brs), 9.42 (0.4H, brs)

REFERENCE PREPARATION EXAMPLE 122-(1)

According to the same manner as that of Reference Preparation Example13,1-[(2-fluoro-3-pyridinyl)methyl]-3-trifluoromethyl-1H-pyrazole-5-carboxylicacid was used in place of1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid to obtain6-chloro-2-[1-[(2-fluoro-3-pyridinyl)methyl]-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[1-[(2-fluoro-3-pyridinyl)methyl]-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.25 (3H, s), 6.16 (2H, s), 7.30-7.36(1H, m), 7.39-7.46 (1H, m), 7.69 (1H, s), 7.90 (1H, d, J=2 Hz), 7.98(1H, d, J=2 Hz), 8.20 (1H, d, J=4 Hz)

REFERENCE PREPARATION EXAMPLE 122-(2)

According to the same manner as that of Reference Preparation Example 1,6-chloro-2-[1-[(2-fluoro-3-pyridinyl)methyl]-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-[(2-fluoro-3-pyridinyl)methyl]-3-trifluoromethyl-1H-pyrazole-5-carboxamideof the formula:

N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-[(2-fluoro-3-pyridinyl)methyl]-3-trifluoromethyl-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.13 (3H, s), 4.37 (2H, brs), 5.86 (2H,s), 7.32-7.38 (2H, m), 7.50-7.57 (2H, m), 7.57-7.64 (1H, m), 8.16-8.21(1H, m), 9.62 (1H, brs), 10.28 (1H, brs)

REFERENCE PREPARATION EXAMPLE 123-(1)

According to the same manner as that of Reference Preparation Example13,1-[(3-chloro-2-pyridinyl)methyl]-5-trifluoromethyl-1H-pyrazole-3-carboxylicacid was used in place of1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid to obtain2-[1-[(3-chloro-2-pyridinyl)methyl]-5-trifluoromethyl-1H-pyrazol-3-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[1-[(3-Chloro-2-pyridinyl)methyl]-5-trifluoromethyl-1H-pyrazol-3-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.56 (3H, s), 5.92 (2H, s), 7.44 (1H, dd,J=8 Hz, 5 Hz), 7.67 (1H, s), 7.89-7.95 (2H, m), 8.04 (1H, d, J=8 Hz),8.42 (1H, d, J=5 Hz)

REFERENCE PREPARATION EXAMPLE 123-(2)

According to the same manner as that of Reference Preparation Example 1,2-[1-[(3-chloro-2-pyridinyl)methyl]-5-trifluoromethyl-1H-pyrazol-3-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-trifluoromethyl-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-[(3-chloro-2-pyridinyl)methyl]-5-trifluoromethyl-1H-pyrazole-3-carboxamideof the formula:

N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-[(3-chloro-2-pyridinyl)methyl]-5-trifluoromethyl-1H-pyrazole-3-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.19 (3H, s), 4.45 (2H, brs), 5.87 (2H,s), 7.37 (1H, brs), 7.41-7.50 (2H, m), 7.52 (1H, brs), 8.04 (1H, d, J=8Hz), 8.45 (1H, d, J=4 Hz), 9.71 (1H, brs), 10.12 (1H, brs)

REFERENCE PREPARATION EXAMPLE 124-(1)

To a solution of 5.0 g of 3-chloro-2-(2-formyl-1H-pyrrol-1-yl)pyridinein 50 ml of N,N-dimethylformamide was added 5.4 g of N-iodosuccinimide.The resulting mixture was stirred at room temperature for 1 day. Waterwas poured into the reaction mixture, and the mixture was extracted withethyl acetate two times. The organic layers were combined, washed withan aqueous saturated sodium chloride solution, dried over anhydrousmagnesium sulfate, and concentrated under reduced pressure. The residuewas subjected to silica gel column chromatography to obtain 3.2 g of1-(3-chloro-2-pyridinyl)-4-iodo-1H-pyrrole-2-carbaldehyde of theformula:

and 0.90 g of 1-(3-chloro-2-pyridinyl)-5-iodo-1H-pyrrole-2-carbaldehydeof the formula:

1-(3-Chloro-2-pyridinyl)-4-iodo-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.19-7.20 (2H, m), 7.38-7.42 (1H, m), 7.89(1H, d, J=8 Hz), 8.45-8.47 (1H, m), 9.51 (1H, s)

1-(3-Chloro-2-pyridinyl)-5-iodo-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.72 (1H, d, J=4 Hz), 7.04 (1H, d, J=4 Hz),7.47 (1H, dd, J=8 Hz, 5 Hz), 7.93 (1H, dd, J=8 Hz, 2 Hz), 8.55 (1H, dd,J=5 Hz, 2 Hz), 9.26 (1H, s)

REFERENCE PREPARATION EXAMPLE 124-(2)

According to the same manner as that of Reference Preparation Example71-(4), 1-(3-chloro-2-pyridinyl)-4-iodo-1H-pyrrole-2-carbaldehyde wasused in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde to obtain1-(3-chloro-2-pyridinyl)-4-iodo-1H-pyrrole-2-carboxylic acid of theformula:

1-(3-Chloro-2-pyridinyl)-4-iodo-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS)_(b)(ppm): 7.05 (1H, d, J=2 Hz), 7.45 (1H, d, J=2Hz), 7.57 (1H, dd, J=8 Hz, 5 Hz), 8.15 (1H, dd, J=8 Hz, 2 Hz), 8.49 (1H,dd, J=5 Hz, 2 Hz), 12.65 (1H, brs)

REFERENCE PREPARATION EXAMPLE 124-(3)

According to the same manner as that of Reference Preparation Example71-(5), 1-(3-chloro-2-pyridinyl)-4-iodo-1H-pyrrole-2-carboxylic acid wasused in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid to obtain6-chloro-2-[1-(3-chloro-2-pyridinyl)-4-iodo-1H-pyrrol-2-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[1-(3-chloro-2-pyridinyl)-4-iodo-1H-pyrrol-2-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.67 (3H, s), 7.30 (1H, d, J=2 Hz), 7.61(1H, d, J=2 Hz), 7.63-7.67 (2H, m), 7.82 (1H, d, J=3 Hz), 8.22 (1H, dd,J=8 Hz, 2 Hz), 8.56 (1H, dd, J=5 Hz, 2 Hz)

REFERENCE PREPARATION EXAMPLE 124-(4)

According to the same manner as that of Reference Preparation Example71-(6),6-chloro-2-[1-(3-chloro-2-pyridinyl)-4-iodo-1H-pyrrol-2-yl]-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-4-iodo-1H-pyrrole-2-carboxamideof the formula:

N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-4-iodo-1H-pyrrole-2-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.13 (3H, s), 4.39 (2H, brs), 7.26 (1H,s), 7.30 (1H, s), 7.39 (1H, s), 7.42 (1H, s), 7.49 (1H, dd, J=8 Hz, 5Hz), 8.05 (1H, dd, J=8 Hz, 2 Hz), 8.43 (1H, dd, J=5 Hz, 2 Hz), 9.52 (1H,brs), 9.84 (1H, brs)

REFERENCE PREPARATION EXAMPLE 125

According to the same manner as that of Reference Preparation Example71-(5), 4,5-dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylicacid and 3-amino-7-bromo-4-chloro-2-naphthoic acid were used in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid and2-amino-5-chloro-3-methylbenzoic acid respectively to obtain10-chloro-2-[4,5-dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-naphtho[2,3-d][1,3]oxazine-4-oneof the formula:

10-Chloro-2-[4,5-dichloro-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-naphtho[2,3-d][1,3]oxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.51 (1H, s), 7.70 (1H, t, J=8 Hz), 7.78(1H, dd, J=8 Hz, 5 Hz), 7.84 (1H, t, J=8 Hz), 8.16 (1H, d, J=8 Hz), 8.28(1H, d, J=8 Hz), 8.40 (1H, dd, J=8 Hz, 2 Hz), 8.68 (1H, dd, J=5 Hz, 2Hz), 8.82 (1H, s)

REFERENCE PREPARATION EXAMPLE 126-(1)

To 30 ml of acetic acid were added 5.0 g of 2-chloro-3-pyridinylamineand 5.6 g of 2,5-dimethoxytetrahydrofuran, and the mixture was heated toreflux for 2 hours. The reaction mixture was allowed to cool to roomtemperature, poured into water, and then extracted with ethyl acetatetwo times. The organic layers were combined, washed successively withwater and an aqueous saturated sodium chloride solution, dried overanhydrous sodium sulfate, and concentrated under reduced pressure. Theresulting residue was subjected to silica gel chromatography to obtain6.5 g of 1-(2-chloro-3-pyridinyl)-1H-pyrrole of the formula:

1-(2-Chloro-3-pyridinyl)-1H-pyrrole

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 6.29 (2H, t, J=2 Hz), 7.09 (2H, t, J=2Hz), 7.58 (1H, dd, J=8H, 5 Hz), 7.95 (1H, dd, J=8H, 2 Hz), 8.45 (1H, dd,J=5H, 2 Hz) Reference Preparation Example 126-(2)

To 14.6 g of N,N-dimethylformamide was added dropwise 8.3 g ofphosphorus oxychloride under ice-cooling. The mixture was stirred atroom temperature for 30 minutes. Thereto 6.5 g of1-(2-chloro-3-pyridinyl)-1H-pyrrole was added, and the resulting mixturewas stirred at 60° C. for 2 hours. The reaction mixture was allowed tocool to room temperature, and added to ice water. The mixture wasadjusted to pH 4 by an addition of a 2N aqueous sodium hydroxidesolution, and then extracted with ethyl acetate two times. The organiclayers were combined, washed successively with water and an aqueoussaturated sodium chloride solution, dried over anhydrous sodium sulfate,and concentrated under reduced pressure. The resulting residue wassubjected to silica gel chromatography to obtain 6.05 g of1-(2-chloro-3-pyridinyl)-1H-pyrrole-2-carbaldehyde of the formula:

1-(2-Chloro-3-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 6.53 (1H, t, J=2 Hz), 7.30 (1H, d, J=2Hz), 7.43 (1H, brs), 7.59 (1H, dd, J=8H, 5 Hz), 8.00 (1H, d, J=8 Hz),8.52 (1H, d, J=5 Hz), 9.51 (1H, s)

REFERENCE PREPARATION EXAMPLE 126-(3)

To a solution of 6.05 g of1-(2-chloro-3-pyridinyl)-1H-pyrrole-2-carbaldehyde in 20 ml ofN,N-dimethylformamide was added 5.72 g of N-bromosuccinimide. Theresulting mixture was stirred at room temperature for 1 hour. Water waspoured into the reaction mixture, and a deposited precipitate wascollected by filtration to obtain 4.22 g of4-bromo-1-(2-chloro-3-pyridinyl)-1H-pyrrole-2-carbaldehyde of theformula:

4-Bromo-1-(2-chloro-3-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.42 (1H, d, J=2 Hz), 7.60 (1H, dd, J=8H,5 Hz), 7.70 (1H, dd, J=2H, 1Hz), 8.06 (1H, dd, J=8H, 2 Hz), 8.54 (1H,dd, J=5H, 2 Hz), 9.47 (1H, d, J=1 Hz)

REFERENCE PREPARATION EXAMPLE 126-(4)

A solution of 4.43 g of potassium permanganate in 15 ml of water wasadded dropwise to a mixture of 4.22 g of4-bromo-1-(2-chloro-3-pyridinyl)-1H-pyrrole-2-carbaldehyde and 30 ml ofacetone while the mixture was maintained at 40° C. The resulting mixturewas stirred at 40° C. for 2 hours. A precipitate was filtered off toobtain a filtrate. The filtrate was adjusted to pH 10-12 by an additionof a 2N aqueous sodium hydroxide solution, and then washed withchloroform two times. The aqueous layer was adjusted to around pH 3 byan addition of 2N hydrochloric acid, and then extracted with ethylacetate two times. The organic layers were combined, washed successivelywith water and an aqueous saturated sodium chloride solution, dried overanhydrous sodium sulfate, and concentrated under reduced pressure toobtain 3.02 g of4-bromo-1-(2-chloro-3-pyridinyl)-1H-pyrrole-2-carboxylic acid of theformula:

4-Bromo-1-(2-chloro-3-pyridinyl)-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.05 (1H, s), 7.46 (1H, s), 7.57 (1H, dd,J=8H, 4 Hz), 8.02 (1H, d, J=8 Hz), 8.49 (1H, d, J=4 Hz), 12.70 (1H, brs)

REFERENCE PREPARATION EXAMPLE 126-(5)

According to the same manner as that of Reference Preparation Example71-(5), 4-bromo-1-(2-chloro-3-pyridinyl)-1H-pyrrole-2-carboxylic acidwas used in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid to obtain2-[4-bromo-1-(2-chloro-3-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[4-Bromo-1-(2-chloro-3-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.65 (3H, s), 7.31 (1H, s), 7.62-7.73(3H, m), 7.84 (1H, s), 8.10 (1H, d, J=6 Hz), 8.57 (1H, s)

REFERENCE PREPARATION EXAMPLE 126-(6)

According to the same manner as that of Reference Preparation Example71-(6),2-[4-bromo-1-(2-chloro-3-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-chloro-3-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

4-Bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-chloro-3-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.14 (3H, s), 4.37 (2H, brs), 7.28 (2H,s), 7.40-7.46 (2H, m), 7.52 (1H, dd, J=8H, 4 Hz), 7.95 (1H, d, J=8Hz),8.42 (1H, d, J=4 Hz), 9.51 (1H, brs), 9.82 (1H, brs)

REFERENCE PREPARATION EXAMPLE 127-(1)

To a mixture of 0.56 g of 3-amino-4-chloro-2-naphthoic acid and 20 ml ofacetic acid was added dropwise 0.4 g of bromine at room temperature. Theresulting mixture was stirred at room temperature for 1 hour. Adeposited precipitate was collected by filtration, and the resultingsolid was washed successively with acetic acid and ethyl acetate toobtain 0.36 g of 3-amino-7-bromo-4-chloro-2-naphthoic acid of theformula:

3-Amino-7-bromo-4-chloro-2-naphthoic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.70 (1H, d, J=9 Hz), 7.81 (1H, d, J=9Hz), 8.24 (1H, s), 8.53 (1H, s)

REFERENCE PREPARATION EXAMPLE 127-(2)

According to the same manner as that of Reference Preparation Example46-(1), 3-amino-7-bromo-4-chloro-2-naphthoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain7-bromo-2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-10-chloro-4H-naphtho[2,3-d][1,3]oxazine-4-oneof the formula:

7-Bromo-2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-10-chloro-4H-naphtho[2,3-d][1,3]oxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.56 (1H, s), 7.75-7.81 (1H, m), 7.99(1H, d, J=10 Hz), 8.14 (1H, d, J=10 Hz), 8.37 (1H, d, J=8 Hz), 8.61-8.68(2H, m), 8.85 (1H, brs)

REFERENCE PREPARATION EXAMPLE 128-(1)

To a mixture of 0.47 g of 3-amino-2-naphthoic acid and 20 ml of aceticacid was added dropwise 0.8 g of bromine at room temperature. Theresulting mixture was stirred at room temperature for 1 hour. Adeposited precipitate was collected by filtration, and the resultingsolid was washed successively with acetic acid and ethyl acetate toobtain 0.61 g of 3-amino-4,7-dibromo-2-naphthoic acid of the formula:

3-Amino-4,7-dibromo-2-naphthoic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.70 (1H, dd, J=9, 2 Hz), 7.80 (1H, d,J=9 Hz), 8.22 (1H, d, J=2 Hz), 8.57 (1H, s)

REFERENCE PREPARATION EXAMPLE 128-(2)

According to the same manner as that of Reference Preparation Example46-(1), 3-amino-4,7-dibromo-2-naphthoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain7,10-dibromo-2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-4H-naphtho[2,3-d][1,3]oxazine-4-oneof the formula:

7,10-Dibromo-2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-4H-naphtho[2,3-d][1,3]oxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.56 (1H, s), 7.76 (1H, dd, J=8 Hz, 5Hz), 7.99 (1H, d, J=9 Hz), 8.14 (1H, d, J=9 Hz), 8.37 (1H, d, J=8 Hz),8.61-8.67 (2H, m), 8.90 (1H, brs)

REFERENCE PREPARATION EXAMPLE 129-(1)

A mixture of 10 g of 2-pyrrolecarbaldehyde, 10 g of 2-fluoropyridine, 24g of cesium carbonate and 100 ml of N-methylpyrrolidone was stirred at120° C. for 1 day. The reaction mixture was allowed to cool to roomtemperature. Water was poured into the mixture, and the mixture wasextracted with ethyl acetate two times. The organic layers werecombined, washed successively with water and an aqueous saturated sodiumchloride solution, dried over magnesium sulfate, and concentrated underreduced pressure. The resulting residue was subjected to silica gelchromatography to obtain 7.7 g of1-(2-pyridinyl)-1H-pyrrole-2-carbaldehyde of the formula:

1-(2-Pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.44 (1H, dd, J=4 Hz, 3 Hz), 7.21 (1H, dd,J=4 Hz, 2 Hz), 7.30-7.33 (1H, m), 7.44-7.47 (2H, m), 7.81-7.86 (1H, m),8.53 (1H, dd, J=5 Hz, 2 Hz), 9.77 (1H, s)

REFERENCE PREPARATION EXAMPLE 129-(2)

According to the same manner as that of Reference Preparation Example97-(1), 1-(2-pyridinyl)-1H-pyrrole-2-carbaldehyde was used in place of3-chloro-2-(2-formyl-1H-pyrrole-1-yl)pyridine to obtain5-chloro-1-(2-pyridinyl)-1H-pyrrole-2-carbaldehyde of the formula:

5-Chloro-1-(2-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.36 (1H, d, J=4 Hz), 7.07 (1H, d, J=4 Hz),7.38 (1H, d, J=8 Hz), 7.44 (1H, dd, J=8 Hz, 5 Hz), 7.87-7.91 (1H, m),8.6.1 (1H, d, J=5 Hz), 9.41 (1H, s)

REFERENCE PREPARATION EXAMPLE 129-(3)

According to the same manner as that of Reference Preparation Example71-(4), 5-chloro-1-(2-pyridinyl)-1H-pyrrole-2-carbaldehyde was used inplace of 4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde toobtain 5-chloro-1-(2-pyridinyl)-1H-pyrrole-2-carboxylic acid of theformula:

5-Chloro-1-(2-pyridinyl)-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 6.36 (1H, d, J=4 Hz), 6.98 (1H, d, J=4Hz), 7.45 (1H, d, J=8 Hz), 7.50-7.53 (1H, m), 7.97-8.00 (1H, m), 8.56(1H, d, J=5 Hz), 12.34 (1H, brs)

REFERENCE PREPARATION EXAMPLE 129-(4)

According to the same manner as that of Reference Preparation Example71-(5), 5-chloro-1-(2-pyridinyl)-1H-pyrrole-2-carboxylic acid was usedin place of 4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylicacid to obtain2-[5-chloro-1-(2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[5-Chloro-1-(2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.70 (3H, s), 6.38 (1H, d, J=4 Hz), 7.29(1H, d, J=4 Hz), 7.38 (1H, s), 7.41-7.49 (2H, m), 7.91-7.94 (2H, m),8.66 (1H, brs)

REFERENCE PREPARATION EXAMPLE 129-(5)

According to the same manner as that of Reference Preparation Example71-(6),2-[5-chloro-1-(2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain5-chloro-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

5-Chloro-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.13 (3H, s), 4.43 (2H, brs), 6.40 (1H,d, J=4 Hz), 7.11 (1H, d, J=4 Hz), 7.30 (1H, d, J=2 Hz), 7.40-7.47 (3H,m), 7.94 (1H, td, J=7 Hz, 2 Hz), 8.51 (1H, dd, J=5 Hz, 2 Hz), 9.51 (1H,brs), 9.85 (1H, brs)

REFERENCE PREPARATION EXAMPLE 130

According to the same manner as that of Reference Preparation Example101,8-bromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain4-bromo-N-[6-bromo-4-chloro-2-(N-methylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

4-Bromo-N-[6-bromo-4-chloro-2-(N-methylhydrazinocarbonyl)phenyl]-1-(3-chlolo-2-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.96 (1.5H, s), 3.15 (1.5H, s), 4.05 (1H,brs), 4.49 (1H, brs), 7.03 (1H, d, J=2 Hz), 7.16 (1H, dd, J=7 Hz, 4 Hz),7.20 (1H, d, J=2 Hz), 7.29-7.34 (1H, m), 7.47 (0.5H, d, J=2 Hz), 7.53(0.5H, d, J=2 Hz), 7.83-7.79 (1H, m), 8.40-8.43 (1H, m), 8.67 (0.5H,brs), 8.77 (0.5H, brs)

REFERENCE PREPARATION EXAMPLE 131-(1)

According to the same manner as that of Reference Preparation Example129-(1), 2-chloro-3-cyanopyridine was used in place of 2-fluoropyridineto obtain 2-(2-formyl-1H-pyrrol-1-yl)-3-cyanopyridine of the formula:

2-(2-Formyl-1H-pyrrol-1-yl)-3-cyanopyridine

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.53 (1H, dd, J=4 Hz, 3 Hz), 7.22 (1H, dd,J=4 Hz, 2 Hz), 7.29-7.31 (1H, m), 7.51 (1H, dd, J=8 Hz, 5 Hz), 8.12 (1H,dd, J=8 Hz, 2 Hz), 8.74 (1H, dd, J=5 Hz, 2 Hz) 9.65 (1H, s)

REFERENCE PREPARATION EXAMPLE 131-(2)

According to the same manner as that of Reference Preparation Example71-(3), 2-(2-formyl-1H-pyrrol-yl)-3-cyanopyridine was used in place of3-chloro-2-(2-formyl-1H-pyrrol-1-yl)pyridine to obtain2-(4-bromo-2-formyl-1H-pyrrol-1-yl)-3-cyanopyridine of the formula:

2-(4-Bromo-2-formyl-1H-pyrrol-1-yl)-3-cyanopyridine

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.18 (1H, d, J=2 Hz), 7.29 (1H, d, J=2 Hz),7.54 (1H, dd, J=8 Hz, 5 Hz), 8.13 (1H, dd, J=8 Hz, 2 Hz), 8.74 (1H, dd,J=5 Hz, 2 Hz), 9.59 (1H, s)

REFERENCE PREPARATION EXAMPLE 131-(3)

According to the same manner as that of Reference Preparation Example71-(4), 2-(4-bromo-2-formyl-1H-pyrrol-1-yl)-3-cyanopyridine was used inplace of 4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde toobtain 4-bromo-1-(3-cyano-2-pyridinyl)-1H-pyrrole-2-carboxylic acid ofthe formula:

4-Bromo-1-(3-cyano-2-pyridinyl)-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.10 (1H, d, J=2 Hz), 7.65 (1H, d, J=2Hz), 7.75 (1H, dd, J=8 Hz, 5 Hz), 8.55 (1H, dd, J=8 Hz, 2 Hz), 8.82 (1H,dd, J=5H z, 2 Hz)

REFERENCE PREPARATION EXAMPLE 131-(4)

According to the same manner as that of Reference Preparation Example71-(5), 4-bromo-1-(3-cyano-2-pyridinyl)-1H-pyrrole-2-carboxylic acid and2-amino-3,5-dibromobenzoic acid were used in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid and2-amino-5-chloro-3-methylbenzoic acid respectively to obtain6,8-dibromo-2-[4-bromo-1-(3-cyano-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-oneof the formula:

6,8-Dibromo-2-[4-bromo-1-(3-cyano-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.39 (1H, d, J=2 Hz), 7.77 (1H, dd, J=8Hz, 5 Hz), 7.81 (1H, d, J=2 Hz), 8.14 (1H, d, J=2 Hz), 8.21 (1H, d, J=2Hz), 8.58 (1H, dd, J=8 Hz, 2 Hz), 8.83 (1H, dd, J=5 Hz, 2 Hz)

REFERENCE PREPARATION EXAMPLE 132-(1)

According to the same manner as that of Reference Preparation Example129-(1), 2-chloro-3-trifluoromethylpyridine was used in place of2-fluoropyridine to obtain1-(3-trifluoromethyl-2-pyridinyl)-1H-pyrrole-2-carbaldehyde of theformula:

1-(3-Trifluoromethyl-2-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.47 (1H, dd, J=4 Hz, 3 Hz), 7.12-7.14 (2H,m), 7.59 (1H, dd, J=8 Hz, 5 Hz), 8.18 (1H, d, J=8 Hz), 8.75 (1H, d, J=5Hz), 9.54 (1H, d, J=1 Hz)

REFERENCE PREPARATION EXAMPLE 132-(2)

According to the same manner as that of Reference Preparation Example71-(3), 1-(3-trifluoromethyl-2-pyridinyl)-1H-pyrrole-2-carbaldehyde wasused in place of 3-chloro-2-(2-formyl-1H-pyrrol-1-yl)pyridine to obtain4-bromo-1-(3-trifluoromethyl-2-pyridinyl)-1H-pyrrole-2-carbaldehyde ofthe formula:

4-Bromo-1-(3-trifluoromethyl-2-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.11 (2H, s), 7.62 (1H, dd, J=8 Hz, 5 Hz),8.18 (1H, d, J=8 Hz), 8.74 (1H, d, J=5 Hz), 9.47 (1H, s)

REFERENCE PREPARATION EXAMPLE 132-(3)

According to the same manner as that of Reference Preparation Example71-(4),4-bromo-1-(3-trifluoromethyl-2-pyridinyl)-1H-pyrrole-2-carbaldehyde wasused in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde to obtain4-bromo-1-(3-trifluoromethyl-2-pyridinyl)-1H-pyrrole-2-carboxylic acidof the formula:

4-Bromo-1-(3-trifluoromethyl-2-pyridinyl)-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.02 (1H, d, J=2 Hz), 7.56 (1H, d, J=2Hz), 7.80 (1H, dd, J=7 Hz, 5 Hz), 8.42 (1H, d, J=7 Hz), 8.82 (1H, d, J=5Hz), 12.66 (1H, brs)

REFERENCE PREPARATION EXAMPLE 132-(4)

According to the same manner as that of Reference Preparation Example71-(5),4-bromo-1-(3-trifluoromethyl-2-pyridinyl)-1H-pyrrole-2-carboxylic acidand 2-amino-3,5-dibromobenzoic acid were used in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid and2-amino-5-chloro-3-methylbenzoic acid respectively to obtain6,8-dibromo-2-[4-bromo-1-(3-trifluoromethyl-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-oneof the formula:

6,8-Dibromo-2-[4-bromo-1-(3-trifluoromethyl-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.34 (1H, s), 7.71 (1H, s), 7.83 (1H, dd,J=8 Hz, 5 Hz), 8.10 (1H, d, J=2 Hz), 8.19 (1H, d, J=2 Hz), 8.48 (1H, d,J=8 Hz), 8.84 (1H, d, J=5 Hz)

REFERENCE PREPARATION EXAMPLE 133-(1)

According to the same manner as that of Reference Preparation Example71-(4), 1-(3-chloro-2-pyridinyl)-5-iodo-1H-pyrrole-2-carbaldehyde wasused in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde to obtain1-(3-chloro-2-pyridinyl)-5-iodo-1H-pyrrole-2-carboxylic acid of theformula:

1-(3-Chloro-2-pyridinyl)-5-iodo-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 6.63 (1H, d, J=4 Hz), 6.97 (1H, d, J=4Hz), 7.62 (1H, dd, J=8 Hz, 5 Hz), 8.20 (1H, d, J=8 Hz), 8.56 (1H, d, J=5Hz), 12.43 (1H, brs)

REFERENCE PREPARATION EXAMPLE 133-(2)

According to the same manner as that of Reference Preparation Example71-(5), 1-(3-chloro-2-pyridinyl)-5-iodo-1H-pyrrole-2-carboxylic acid wasused in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid to obtain6-chloro-2-[1-(3-chloro-2-pyridinyl)-5-iodo-1H-pyrrol-2-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[1-(3-chloro-2-pyridinyl)-5-iodo-1H-pyrrol-2-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.65 (3H, s), 6.82 (1H, d, J=3 Hz), 7.23(1H, d, J=3 Hz), 7.67 (1H, s), 7.71 (1H, dd, J=8 Hz, 5 Hz), 7.81 (1H,s), 8.32 (1H, d, J=8 Hz), 8.65 (1H, d, J=5 Hz)

REFERENCE PREPARATION EXAMPLE 133-(3)

According to the same manner as that of Reference Preparation Example71-(6),6-chloro-2-[1-(3-chloro-2-pyridinyl)-5-iodo-1H-pyrrol-2-yl]-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtainN-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-5-iodo-1H-pyrrole-2-carboxamideof the formula:

N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-5-iodo-1H-pyrrole-2-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.16 (3H, s), 4.02 (2H, brs), 6.66 (1H, s),7.05 (1H, s), 7.19 (1H, s), 7.24 (1H, s), 7.37 (1H, dd, J=8 Hz, 5 Hz),7.50 (1H, brs), 7.86 (1H, d, J=8 Hz), 8.49 (1H, d, J=5 Hz), 9.28 (1H,brs)

REFERENCE PREPARATION EXAMPLE 134-(1)

A mixture of 1.51 g of 2-amino-3-methylbenzoic acid, 1.0 g of aceticanhydride and 20 ml of tetrahydrofuran was stirred at 80° C. for 13hours. The reaction mixture was allowed to cool to room temperature,poured into water, and extracted with ethyl acetate two times. Theorganic layers were combined, washed successively with water and anaqueous saturated sodium chloride solution, dried over anhydrous sodiumsulfate, and concentrated under reduced pressure. The resulting residuewas washed with ethyl acetate to obtain 0.72 g of2-acetylamino-3-methylbenzoic acid of the formula:

2-Acetylamino-3-methylbenzoic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.00 (3H, s), 2.19 (3H, s), 7.21 (1H, t,J=8 Hz), 7.41 (1H, d, J=8 Hz), 7.58 (1H, d, J=8 Hz), 9.47 (1H, brs)

REFERENCE PREPARATION EXAMPLE 134-(2)

To a mixture of 0.72 g of 2-acetylamino-3-methylbenzoic acid and 8 ml ofconcentrated sulfuric acid was added dropwise 1.6 g of fuming nitricacid at room temperature. The resulting mixture was stirred at roomtemperature for 2 hours. The reaction mixture was poured into ice water.A deposited precipitate was collected by filtration to obtain 0.45 g of2-acetylamino-3-methyl-5-nitrobenzoic acid of the formula:

2-Acetylamino-3-methyl-5-nitrobenzoic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.06 (3H, s), 2.34 (3H, s), 8.31 (2H, s),9.93 (1H, brs)

REFERENCE PREPARATION EXAMPLE 134-(3)

A mixture of 0.45 g of 2-acetylamino-3-methyl-5-nitrobenzoic acid, 0.45g of potassium hydroxide, 5 ml of methanol and 20 ml of water was heatedto reflux at 80° C. for 2 hours. The reaction mixture was allowed tocool to room temperature, and water was poured into the mixture. Themixture was adjusted to pH 3 by an addition of 2N hydrochloric acid. Adeposited precipitate was collected by filtration to obtain 0.28 g of2-amino-3-methyl-5-nitrobenzoic acid of the formula:

2-Amino-3-methyl-5-nitrobenzoic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.19 (3H, s), 7.99 (1H, s), 8.56 (1H, s)

REFERENCE PREPARATION EXAMPLE 134-(4)

According to the same manner as that of Reference Preparation Example46-(1), 2-amino-3-methyl-5-nitrobenzoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-methyl-6-nitro-4H-3,1-benzoxazine-4-oneof the formula:

2-[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-8-methyl-6-nitro-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.81 (3H, s), 7.64 (1H, s), 7.79 (1H, dd,J=8 Hz, 4 Hz), 8.38 (1H, d, J=8 Hz), 8.48 (1H, s), 8.55 (1H, s), 8.64(1H, d, J=4 Hz)

REFERENCE PREPARATION EXAMPLE 135-(1)

According to the same manner as that of Reference Preparation Example129-(1), 2-chloro-3-nitropyridine was used in place of 2-fluoropyridineto obtain 1-(3-nitro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde of theformula:

1-(3-Nitro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.54 (1H, dd, J=4 Hz, 3 Hz), 7.18 (1H, dd,J=4 Hz, 2 Hz), 7.34-7.35 (1H, m), 7.60 (1H, dd, J=8 Hz, 5 Hz), 8.51 (1H,dd, J=8 Hz, 2 Hz), 8.75 (1H, dd, J=5 Hz, 2 Hz), 9.48 (1H, d, J=1 Hz)

REFERENCE PREPARATION EXAMPLE 135-(2)

According to the same manner as that of Reference Preparation Example71-(3), 1-(3-nitro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde was used inplace of 3-chloro-2-(2-formyl-1H-pyrrol-1-yl)pyridine to obtain4-bromo-1-(3-nitro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde of theformula:

4-Bromo-1-(3-nitro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.14 (1H, d, J=2 Hz), 7.33 (1H, d, J=2 Hz),7.63 (1H, dd, J=8 Hz, 5 Hz), 8.53 (1H, dd, J=8 Hz, 2 Hz), 8.75 (1H, dd,J=5 Hz, 2 Hz), 9.42 (1H, s)

REFERENCE PREPARATION EXAMPLE 135-(3)

According to the same manner as that of Reference Preparation Example71-(4), 4-bromo-1-(3-nitro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde wasused in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde to obtain4-bromo-1-(3-nitro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid of theformula:

4-Bromo-1-(3-nitro-2-pyridinyl)-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.05 (1H, d, J=2 Hz), 7.60 (1H, d, J=2Hz), 7.84 (1H, dd, J=8 Hz, 5 Hz), 8.68 (1H, d, J=8 Hz, 2 Hz), 8.84 (1H,d, J=5 Hz, 2 Hz)

REFERENCE PREPARATION EXAMPLE 135-(4)

According to the same manner as that of Reference Preparation Example71-(5), 4-bromo-1-(3-nitro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid and2-amino-3,5-dibromobenzoic acid were used in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid and2-amino-5-chloro-3-methylbenzoic acid respectively to obtain6,8-dibromo-2-[4-bromo-1-(3-nitro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-oneof the formula:

6,8-Dibromo-2-[4-bromo-1-(3-nitro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.38 (1H, d, J=2 Hz), 7.80 (1H, d, J=2Hz), 7.92 (1H, dd, J=8 Hz, 5 Hz), 8.11 (1H, d, J=2 Hz), 8.26 (1H, d, J=2Hz), 8.84 (1H, d, J=8 Hz), 8.65 (1H, d, J=5 Hz)

REFERENCE PREPARATION EXAMPLE 136-(1)

According to the same manner as that of Reference Preparation Example129-(1), 3-bromo-2-chloropyridine was used in place of 2-fluoropyridineto obtain 1-(3-bromo-2-pyridinyl)-1H-pyrrole-2-carbaldehyde of theformula:

1-(3-Bromo-2-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.48 (1H, dd, J=4 Hz, 3 Hz), 7.10-7.17 (2H,m), 7.31 (1H, dd, J=8 Hz, 5 Hz), 8.05 (1H, dd, J=8 Hz, 2 Hz), 8.51 (1H,dd, J=5 Hz, 2 Hz), 9.57 (1H, s)

REFERENCE PREPARATION EXAMPLE 136-(2)

According to the same manner as that of Reference Preparation Example71-(3), 1-(3-bromo-2-pyridinyl)-1H-pyrrole-2-carbaldehyde was used inplace of 3-chloro-2-(2-formyl-1H-pyrrol-1-yl)pyridine to obtain4-bromo-1-(3-bromo-2-pyridinyl)-1H-pyrrole-2-carbaldehyde of theformula:

4-Bromo-1-(3-bromo-2-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.11-7.14 (2H, m), 7.33 (1H, dd, J=8 Hz, 5Hz), 8.06 (1H, dd, J=8 Hz, 2 Hz), 8.50 (1H, dd, J=5 Hz, 2 Hz), 9.50 (1H,d, J=1 Hz)

REFERENCE PREPARATION EXAMPLE 136-(3)

According to the same manner as that of Reference Preparation Example71-(4), 4-bromo-1-(3-bromo-2-pyridinyl)-1H-pyrrole-2-carbaldehyde wasused in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde to obtain4-bromo-1-(3-bromo-2-pyridinyl)-1H-pyrrole-2-carboxylic acid of theformula:

4-Bromo-1-(3-bromo-2-pyridinyl)-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.01 (1H, s), 7.48-7.51 (2H, m), 8.28(1H, d, J=8 Hz), 8.52 (1H, d, J=5 Hz), 12.67 (1H, brs)

REFERENCE PREPARATION EXAMPLE 136-(4)

According to the same manner as that of Reference Preparation Example71-(5), 4-bromo-1-(3-bromo-2-pyridinyl)-1H-pyrrole-2-carboxylic acid and2-amino-3,5-dibromobenzoic acid were used in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid and2-amino-5-chloro-3-methylbenzoic acid respectively to obtain6,8-dibromo-2-[4-bromo-1-(3-bromo-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-oneof the formula:

6,8-Dibromo-2-[4-bromo-1-(3-bromo-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.33 (1H, s), 7.53 (1H, dd, J=8 Hz, 5Hz), 7.72 (1H, s), 8.12 (1H, d, J=2 Hz), 8.27 (1H, d, J=2 Hz), 8.36 (1H,d, J=8 Hz), 8.57 (1H, d, J=5 Hz)

REFERENCE PREPARATION EXAMPLE 137-(1)

A mixture of 2.0 g of 2-pyrrole carbaldehyde, 3.0 g of3,4-dichloropyridine, 8.0 g of cesium carbonate and 30 ml ofN-methylpyrrolidone was stirred at 120° C. for 25 hours. The reactionmixture was allowed to cool room temperature, and water was poured intothe mixture. The mixture was extracted with ethyl acetate two times. Theorganic layers were combined, washed successively with water and anaqueous saturated sodium chloride solution, dried over anhydrous sodiumsulfate, and concentrated under reduced pressure. The resulting residuewas subjected to silica gel chromatography to obtain 2.95 g of1-(3-chloro-4-pyridinyl)-1H-pyrrole-2-carbaldehyde of the formula:

1-(3-Chloro-4-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 6.55 (1H, dd, J=4 Hz, 3 Hz), 7.33 (1H,dd, J=4 Hz, 2 Hz), 7.44 (1H, ddd, J=3 Hz, 2 Hz, 1Hz), 7.60 (1H, d, J=5Hz), 8.66 (1H, d, J=5 Hz), 8.83 (1H, s), 9.52 (1H, d, J=1 Hz)

REFERENCE PREPARATION EXAMPLE 137-(2)

To a solution of 2.95 g of1-(3-chloro-4-pyridinyl)-1H-pyrrole-2-carbaldehyde in 20 ml ofN,N-dimethylformamide was added 2.66 g of N-bromosuccinimide. Theresulting mixture was stirred at room temperature for 10 hours. Waterwas poured into the reaction mixture, and a deposited precipitate wascollected by filtration to obtain 1.2 g of4-bromo-1-(3-chloro-4-pyridinyl)-1H-pyrrole-2-carbaldehyde of theformula:

4-Bromo-1-(3-chloro-4-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.44-7.46 (1H, m), 7.66 (1H, d, J=5 Hz),7.69-7.72 (1H, m), 8.68 (1H, d, J=5 Hz), 8.85 (1H, s), 9.47 (1H, s)

REFERENCE PREPARATION EXAMPLE 137-(3)

A solution of 2.0 g of potassium permanganate in 10 ml of water wasadded dropwise to a mixture of 1.2 g of4-bromo-1-(3-chloro-4-pyridinyl)-1H-pyrrole-2-carbaldehyde and 30 ml ofacetone while the mixture was maintained at 40° C. The resulting mixturewas stirred at 60° C. for 1 hour. A precipitate was filtered off toobtain a filtrate. The filtrate was adjusted to pH 10-12 by an additionof a 2N aqueous sodium hydroxide solution, and then washed withchloroform two times. The aqueous layer was adjusted to around pH 3 byan addition of 2N hydrochloric acid, and then extracted with ethylacetate two times. The organic layers were combined, washed successivelywith water and an aqueous saturated sodium chloride solution, dried overanhydrous sodium sulfate, and concentrated under reduced pressure toobtain 0.43 g of4-bromo-1-(3-chloro-4-pyridinyl)-1H-pyrrole-2-carboxylic acid of theformula:

4-Bromo-1-(3-chloro-4-pyridinyl)-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.07 (1H, d, J=2 Hz), 7.47 (1H, d, J=2Hz), 7.63 (1H, d, J=5 Hz), 8.65 (1H, d, J=5 Hz), 8.81 (1H, s)

REFERENCE PREPARATION EXAMPLE 137-(4)

According to the same manner as that of Reference Preparation Example71-(5), 4-bromo-1-(3-chloro-4-pyridinyl)-1H-pyrrole-2-carboxylic acidwas used in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid to obtain2-[4-bromo-1-(3-chloro-4-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

2-[4-Bromo-1-(3-chloro-4-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.63 (3H, s), 7.33 (1H, d, J=2 Hz),7.68-7.74 (3H, m), 7.85 (1H, d, J=2 Hz), 8.73 (1H, d, J=5 Hz), 8.91 (1H,s)

REFERENCE PREPARATION EXAMPLE 137-(5)

According to the same manner as that of Reference Preparation Example71-(6),2-[4-bromo-1-(3-chloro-4-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain4-bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-4-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

4-Bromo-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(3-chloro-4-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.15 (3H, s), 4.39 (2H, brs), 7.27-7.31(2H, m), 7.42-7.46 (2H, m), 7.56 (1H, d, J=5 Hz), 8.60 (1H, d, J=5 Hz),8.72 (1H, s), 9.54 (1H, brs), 9.87 (1H, brs)

REFERENCE PREPARATION EXAMPLE 138-(1)

According to the same manner as that of Reference Preparation Example46-(1), 2-amino-5-chloro-benzoic acid was used in place of2-amino-3,5-dibromobenzoic acid to obtain2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-6-chloro-4H-3,1-benzoxazine-4-oneof the formula:

2-[3-Bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-yl]-6-chloro-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.01 (1H, d, J=9 Hz), 7.53 (1H, s), 7.78(1H, dd, J=8 Hz, 5 Hz), 7.88 (1H, dd, J=9 Hz, 3 Hz), 8.06 (1H, d, J=3Hz), 8.32 (1H, dd, J=8 Hz, 1Hz), 8.60 (1H, dd, J=5 Hz, 1Hz).

REFERENCE PREPARATION EXAMPLE 139

According to the same manner as that of Reference Preparation Example84,2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain3-bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideof the formula:

3-Bromo-N-[4-chloro-2-(N-methylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.88 (0.6H, s), 3.10 (2.4H, s), 4.71(1.6H, s), 5.01 (0.4H, s), 7.29-7.34 (1.0H, brm), 7.38-7.52 (3.0H, m),7.65 (1.0H, dd, J=8 Hz, 5 Hz), 8.22 (1.0H, dd, J=8 Hz, 2 Hz), 8.52(1.0H, dd, J=5 Hz, 2 Hz), 10.40-10.50 (1.0H, brm).

REFERENCE PREPARATION EXAMPLE 140

According to the same manner as that of Reference Preparation Example88,2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-4H-3,1-benzoxazine-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain3-bromo-N-[4-chloro-2-(N,N′-dimethylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideof the formula:

3-Bromo-N-[4-chloro-2-(N,N′-dimethylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.69 (3H, brs), 3.28 (3H, s), 6.92 (1H, s),7.30-7.46 (3H, m), 7.91 (1H, dd, J=8 Hz, 2 Hz), 8.17 (1H, d, J=9 Hz),8.49 (1H, dd, J=5 Hz, 2 Hz), 10.29 (1H, brs).

REFERENCE PREPARATION EXAMPLE 141-(1)

According to the same manner as that of Reference Preparation ExamplePreparation Example 100-(1), 2-(2-FORMYL-1H-pyrrol-1-yl)pyridine wasused in place of 3-chloro-2-(2-formyl-1H-pyrrol-1-yl)pyridine to obtain4,5-dichloro-1-(2-pyridinyl)-1H-pyrrole-2-carbaldehyde of the formula:

and 3,5-dichloro-1-(2-pyridinyl)-1H-pyrrole-2-carbaldehyde of theformula:

4,5-Dichloro-1-(2-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.08 (1H, s), 7.38-7.41 (1H, m), 7.47-7.50(1H, m), 7.91-7.95 (1H, m), 8.63-8.65 (1H, m), 9.40 (1H, s)

3,5-Dichloro-1-(2-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.35 (1H, s), 7.33-7.36 (1H, m), 7.45-7.48(1H, m), 7.89-7.93 (1H, m), 8.61-8.62 (1H, m), 9.64 (1H, s)

REFERENCE PREPARATION EXAMPLE 141-(2)

According to the same manner as that of Reference Preparation Example71-(4), 4,5-dichloro-1-(2-pyridinyl)-1H-pyrrole-2-carbaldehyde was usedin place of 4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehydeto obtain 4,5-dichloro-1-(2-pyridinyl)-1H-pyrrole-2-carboxylic acid ofthe formula:

4,5-Dichloro-1-(2-pyridinyl)-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.11 (1H, s), 7.56-7.58 (2H, m), 8.03(1H, td, J=8 Hz, 2 Hz), 8.58 (1H, dd, J=4 Hz, 2 Hz)

REFERENCE PREPARATION EXAMPLE 141-(3)

According to the same manner as that of Reference Preparation Example71-(5), 4,5-dichloro-1-(2-pyridinyl)-1H-pyrrole-2-carboxylic acid wasused in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid to obtain6-chloro-2-[4,5-dichloro-1-(2-pyridinyl)-1H-pyrrol-2-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[4,5-dichloro-1-(2-pyridinyl)-1H-pyrrol-2-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.07 (3H, s), 7.35 (1H, s), 7.62-7.67(3H, m), 7.81 (1H, s), 8.11 (1H, t, J=8 Hz), 8.65 (1H, d, J=5 Hz)

REFERENCE PREPARATION EXAMPLE 141-(4)

According to the same manner as that of Reference Preparation Example71-(6),6-chloro-2-[4,5-dichloro-1-(2-pyridinyl)-1H-pyrrol-2-yl]-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain4,5-dichloro-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

4,5-Dichloro-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.16 (3H, s), 7.01 (1H, s), 7.25 (2H, s),7.36-7.41 (2H, m), 7.87 (1H, td, J=8 Hz, 2 Hz), 7.95 (1H, brs),8.55-8.57 (1H, m), 9.42 (1H, brs)

REFERENCE PREPARATION EXAMPLE 142-(1)

According to the same manner as that of Reference Preparation Example71-(4), 3,5-dichloro-1-(2-pyridinyl)-1H-pyrrole-2-carbaldehyde was usedin place of 4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehydeto obtain 3,5-dichloro-1-(2-pyridinyl)-1H-pyrrole-2-carboxylic acid ofthe formula:

3,5-Dichloro-1-(2-pyridinyl)-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 6.64 (1H, s), 7.53-7.57 (2H, m), 8.02(1H, td, J=8 Hz, 2 Hz), 8.55-8.57 (1H, m)

REFERENCE PREPARATION EXAMPLE 142-(2)

According to the same manner as that of Reference Preparation Example71-(5), 3,5-dichloro-1-(2-pyridinyl)-1H-pyrrole-2-carboxylic acid wasused in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid to obtain6-chloro-2-[3,5-dichloro-1-(2-pyridinyl)-1H-pyrrol-2-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[3,5-dichloro-1-(2-pyridinyl)-1H-pyrrol-2-yl]-8-methyl-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.82 (3H, s), 6.97 (1H, s), 7.60-7.70(3H, m), 7.81-7.83 (1H, m), 8.04-8.12 (1H, m), 8.58 (1H, d, J=6 Hz)

REFERENCE PREPARATION EXAMPLE 142-(3)

According to the same manner as that of Reference Preparation Example71-(6),6-chloro-2-[3,5-dichloro-1-(2-pyridinyl)-1H-pyrrol-2-yl]-8-methyl-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain3,5-dichloro-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

3,5-D-chloro-N-[4-chloro-2-(hydrazinocarbonyl)-6-methylphenyl]-1-(2-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.14 (3H, s), 6.26 (1H, s), 7.20-7.23 (2H,s), 7.28-7.34 (2H, m), 7.61-7.65 (1H, m), 7.76-7.81 (1H, m), 8.49 (1H,brs), 8.79 (1H, brs)

REFERENCE PREPARATION EXAMPLE 143-(1)

To a solution of 3.0 g of3-chloro-2-(4-bromo-2-formyl-1H-pyrrol-1-yl)-pyridine in 30 ml oftetrahydrofuran was added 1.5 g of N-chlorosuccinimide. The resultingmixture was stirred at room temperature for 2 days. Water was pouredinto the reaction mixture, and the mixture was extracted with ethylacetate two times. The organic layers were combined, washed with anaqueous saturated sodium chloride solution, dried over anhydrousmagnesium sulfate, and concentrated under reduced pressure. The residuewas subjected to silica gel column chromatography to obtain 2.5 g of4-bromo-5-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde ofthe formula:

4-Bromo-5-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.12 (1H, s), 7.47 (1H, dd, J=8 Hz, 5 Hz),7.94 (1H, dd, J=8 Hz, 2 Hz), 8.53 (1H, dd, J=5 Hz, 2 Hz), 9.38 (1H, s)

REFERENCE PREPARATION EXAMPLE 143-(2)

According to the same manner as that of Reference Preparation Example71-(4),4-bromo-5-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde wasused in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde to obtain4-bromo-5-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acidof the formula:

4-Bromo-5-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.20 (1H, s), 7.67 (1H, dd, J=8 Hz, 5Hz), 8.25 (1H, dd, J=8 Hz, 2 Hz), 8.58 (1H, dd, J=5 Hz, 2 Hz), 12.99(1H, brs)

REFERENCE PREPARATION EXAMPLE 143-(3)

According to the same manner as that of Reference Preparation Example71-(5),4-bromo-5-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acidand 2-amino-3,5-dibromobenzoic acid were used in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid and2-amino-5-chloro-3-methylbenzoic acid respectively to obtain2-[4-bromo-5-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6,8-dibromo-4H-3,1-benzoxazine-4-oneof the formula:

2-[4-Bromo-5-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6,8-dibromo-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.49 (1H, s), 7.71 (1H, dd, J=8 Hz, 5 Hz),8.11 (1H, d, J=2 Hz), 8.26 (1H, d, J=2 Hz), 8.34 (1H, dd, J=8 Hz, 1Hz),8.63 (1H, dd, J=5 Hz, 1Hz)

REFERENCE PREPARATION EXAMPLE 143-(4)

According to the same manner as that of Reference Preparation Example71-(6),2-[4-bromo-5-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6,8-dibromo-4H-3,1-benzoxazine-4-onewas used in place of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-6-chloro-8-methyl-4H-3,1-benzoxazine-4-oneto obtain4-bromo-N-[4,6-dibromo-2-(hydrazinocarbonyl)phenyl]-5-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

4-Bromo-N-[4,6-dibromo-2-(hydrazinocarbonyl)phenyl]-5-chloro-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.21 (1H, s), 7.39 (1H, dd, J=8 Hz, 5 Hz),7.42 (1H, d, J=2 Hz), 7.70 (1H, d, J=2 Hz), 7.88 (1H, dd, J=8 Hz, 2 Hz),8.49 (1H, dd, J=5 Hz, 2 Hz), 8.71 (1H, s)

REFERENCE PREPARATION EXAMPLE 144

Under ice-cooling, 8.42 g of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6,8-dibromo-4H-3,1-benzoxazine-4-one,3.0 g of hydrazine monohydrate and 60 ml of tetrahydrofuran were mixed,and the mixture was stirred at room temperature for 3 hours. A depositedprecipitate was collected by filtration, and washed successively withtetrahydrofuran and methyl t-butyl ether to obtain 4.85 g of3-bromo-N-[4,6-dibromo-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideof the formula:

3-Bromo-N-[4,6-dibromo-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 4.35 (2H, brs), 7.42 (1H, s), 7.58-7.62(2H, m), 8.07 (1H, d, J=2 Hz), 8.16 (1H, dd, J=8 Hz, 2 Hz), 8.50 (1H,dd, J=5 Hz, 2 Hz), 9.61 (1H, brs)

REFERENCE PREPARATION EXAMPLE 145

A mixture of 0.50 g of6,8-dibromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-one,0.15 ml of methylhydrazine and 8 ml of tetrahydrofuran was stirred atroom temperature for 20 hours. Water was poured into the reactionmixture, and the mixture was extracted with ethyl acetate. The organiclayer was washed successively with water and an aqueous saturated sodiumchloride solution, dried over anhydrous magnesium sulfate, andconcentrated under reduced pressure. The resulting residue was subjectedto silica gel chromatography to obtain 0.39 g of4-bromo-N-[4,6-dibromo-2-(N-methylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

4-Bromo-N-[4,6-dibromo-2-(N-methylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.96 (1.5H, s), 3.15 (1.5H, s), 4.05 (1.0H,s), 4.48 (1.0H, s), 7.03 (1.0H, d, J=2 Hz), 7.18 (0.5H, d, J=2 Hz), 7.21(0.5H, d, J=2 Hz), 7.29-7.34 (2.0H, m), 7.63 (0.5H, d, J=2 Hz), 7.68(0.5H, d, J=2 Hz), 7.79-7.83 (1.0H, m), 8.40-8.44 (1.0H, m), 8.67 (0.5H,s), 8.77 (0.5H, s)

REFERENCE PREPARATION EXAMPLE 146

A mixture of 1.0 g of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6,8-dibromo-4H-3,1-benzoxazine-4-one,0.28 ml of methylhydrazine and 16 ml of tetrahydrofuran was stirred atroom temperature for 19 hours. Water was poured into the reactionmixture, and the mixture was extracted with ethyl acetate. The organiclayer was washed successively with water and an aqueous saturated sodiumchloride solution, dried over anhydrous magnesium sulfate, andconcentrated under reduced pressure. The resulting residue was subjectedto silica gel chromatography to obtain 0.97 g of3-bromo-N-[4,6-dibromo-2-(N-methylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideof the formula:

3-Bromo-N-[4,6-dibromo-2-(N-methylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.97 (1.5H, s), 3.17 (1.5H, s), 3.99 (1.0H,s), 4.51 (1.0H, s), 7.31 (1.0H, d, J=2 Hz), 7.35-7.41 (2.0H, m), 7.61(0.5H, d, J=2 Hz), 7.67 (0.5H, d, J=2 Hz), 7.84-7.89 (1.0H, m),8.45-8.50 (1.0H, m), 9.32 (0.5H, s), 9.45 (0.5H, s)

REFERENCE PREPARATION EXAMPLE 147

To a mixture of 0.42 g of N,N′-dimethylhydrazine dihydrochloride, fivedrops of water, 0.87 g of potassium carbonate and 10 ml oftetrahydrofuran was added 0.60 g of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6,8-dibromo-4H-3,1-benzoxazine-4-one.The resulting mixture was stirred at room temperature for 19 hours.Water was poured into the reaction mixture, and the mixture wasextracted with ethyl acetate. The organic layer was washed successivelywith water and an aqueous saturated sodium chloride solution, dried overanhydrous magnesium sulfate, and concentrated under reduced pressure.The resulting residue was subjected to silica gel chromatography toobtain 0.51 g of3-bromo-N-[4,6-dibromo-2-(N,N′-dimethylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideof the formula:

3-Bromo-N-[4,6-dibromo-2-(N,N′-dimethylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.49 (1.5H, d, J=6 Hz), 2.58 (1.5H, d, J=6Hz), 2.92 (1.5H, s), 3.11 (1.5H, s), 3.52 (0.5H, q, J=6 Hz), 5.43 (0.5H,q, J=6 Hz), 7.21 (0.5H, s), 7.24 (0.5H, s), 7.30 (0.5H, d, J=2 Hz), 7.32(0.5H, d, J=2 Hz), 7.35-7.39 (1.0H, m), 7.61 (0.5H, d, J=2 Hz), 7.67(0.5H, d, J=2 Hz), 7.83-7.87 (1.0H, m), 8.44-8.47 (1.0H, m), 9.24 (0.5H,s), 9.42 (0.5H, s)

REFERENCE PREPARATION EXAMPLE 148

To a mixture of 0.42 g of N,N′-dimethylhydrazine dihydrochloride, fivedrops of water, 0.87 g of potassium carbonate and 10 ml oftetrahydrofuran was added 0.59 g of6,8-dibromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-one.The resulting mixture was stirred at room temperature for 2 hours. Waterwas poured into the reaction mixture, and the mixture was extracted withethyl acetate. The organic layer was washed successively with water andan aqueous saturated sodium chloride solution, dried over anhydrousmagnesium sulfate, and concentrated under reduced pressure. Theresulting residue was subjected to silica gel chromatography to obtain0.52 g of4-bromo-N-[4,6-dibromo-2-(N,N′-dimethylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

4-Bromo-N-[4,6-dibromo-2-(N,N′-dimethylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamide

¹H-NMR (CDCl₃) δ:2.47 (1.5H, d, J=6 Hz), 2.55 (1.5H, brs), 2.91 (1.5H,s), 3.08 (1.5H, s), 3.54 (0.5H, q, J=6 Hz), 5.46 (0.5H, brs), 7.03(1.0H, d, J=2 Hz), 7.10 (0.5H, d, J=2 Hz), 7.15 (0.5H, d, J=2 Hz),7.28-7.32 (2.0H, m), 7.65 (0.5H, d, J=2 Hz), 7.69 (0.5H, d, J=2 Hz),7.77-7.81 (1.0H, m), 8.39-8.41 (1.5H, m), 8.62 (0.5H, s).

REFERENCE PREPARATION EXAMPLE 149-(1)

To 10 ml of methanol were added 1.0 g of3-chloro-2-(2-formyl-1H-pyrrol-1-yl)pyridine and 1.4 g of sodiumthiocyanate. A solution of 1.0 g of bromine in 5 ml of saturated sodiumbromide-methanol was added dropwise thereto at −20° C. The resultingmixture was stirred at the same temperature for 2 hours. The reactionmixture was added to 100 ml of ice water, and extracted with chloroformtwo times. The organic layers were combined, washed with an aqueoussaturated sodium chloride solution, dried over anhydrous magnesiumsulfate, and concentrated under reduced pressure to obtain 1.6 g of1-(3-chloro-2-pyridinyl)-5-thiocyanato-1H-pyrrole-2-carbaldehyde of theformula:

1-(3-Chloro-2-pyridinyl)-5-thiocyanato-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.95 (1H, d, J=4 Hz), 7.16 (1H, d, J=4 Hz),7.52 (1H, dd, J=8 Hz, 5 Hz), 7.97 (1H, dd, J=8 Hz, 2 Hz), 8.57 (1H, dd,J=5 Hz, 2 Hz), 9.58 (1H, s)

REFERENCE PREPARATION EXAMPLE 149-(2)

According to the same manner as that of Reference Preparation Example71-(4), 1-(3-chloro-2-pyridinyl)-5-thiocyanato-1H-pyrrole-2-carbaldehydewas used in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carbaldehyde to obtain1-(3-chloro-2-pyridinyl)-5-thiocyanato-1H-pyrrole-2-carboxylic acid ofthe formula:

1-(3-Chloro-2-pyridinyl)-5-thiocyanato-1H-pyrrole-2-carboxylic Acid

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.07 (1H, d, J=4 Hz), 7.11 (1H, d, J=4Hz), 7.69 (1H, dd, J=8 Hz, 5 Hz), 8.27 (1H, d, J=8 Hz), 8.62 (1H, d, J=5Hz)

REFERENCE PREPARATION EXAMPLE 149-(3)

According to the same manner as that of Reference Preparation Example71-(5), 1-(3-chloro-2-pyridinyl)-5-thiocyanato-1H-pyrrole-2-carboxylicacid and 2-amino-3,5-dibromobenzoic acid were used in place of4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxylic acid and2-amino-5-chloro-3-methylbenzoic acid respectively to obtain6,8-dibromo-2-[1-(3-chloro-2-pyridinyl)-5-thiocyanato-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-oneof the formula:

6,8-Dibromo-2-[1-(3-chloro-2-pyridinyl)-5-thiocyanato-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.23 (1H, d, J=4 Hz), 7.41 (1H, d, J=4Hz), 7.72 (1H, dd, J=8 Hz, 5 Hz), 8.14 (1H, d, J=2 Hz), 8.29 (1H, d, J=2Hz), 7.34 (1H, d, J=8 Hz), 8.66 (1H, d, J=5 Hz)

REFERENCE PREPARATION EXAMPLE 150

Under ice-cooling, 0.569 g of6,8-dibromo-2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-one,0.20 g of hydrazine monohydrate and 2 ml of tetrahydrofuran were mixed,and the mixture was stirred at room temperature for 1 hour. Water waspoured into the reaction mixture, and the mixture was extracted withethyl acetate. The organic layer was washed with water, dried oversodium sulfate, and concentrated under reduced pressure to obtain 0.53 gof4-bromo-N-[4,6-dibromo-2-(hydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrrole-2-carboxamideof the formula:

REFERENCE PREPARATION EXAMPLE 151-(1)

A mixture of 1.0 g of 4-bromoimidazole, 1.3 g of3-chloro-2-(methanesulfonyl)pyridine, 2.7 g of cesium carbonate and 10ml of N,N-dimethylformamide was stirred at 100° C. for 6 hours. Thereaction mixture was allowed to cool to room temperature, and water waspoured into the mixture. A deposited precipitate was collected byfiltration to obtain 1.7 g of2-(4-bromo-1H-imidazol-1-yl)-3-chloropyridine of the formula:

2-(4-Bromo-1H-imidazol-1-yl)-3-chloropyridine

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.33 (1H, dd, J=8 Hz, 5 Hz), 7.63 (1H, s),7.93 (1H, dd, J=8 Hz, 2 Hz), 8.13 (1H, s), 8.45-8.46 (1H, m)

REFERENCE PREPARATION EXAMPLE 151-(2)

To a solution of 1.0 g of 2-(4-bromo-1H-imidazol-1-yl)-3-chloropyridinein 5 ml of dichloromethane was added dropwise a solution of 0.45 ml oftrichloroacetyl chloride in 5 ml of dichloromethane at room temperature.The resulting mixture was stirred at room temperature for 1 day. Thereto0.57 ml of triethylamine was added, and the resulting mixture wasstirred at room temperature for 2 hours. The reaction mixture wasconcentrated under reduced pressure, and the resulting residue wassubjected to silica gel chromatography to obtain 1.0 g of1-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-imidazol-2-yl]-2,2,2-trichloroethanoneof the formula:

1-[4-Bromo-1-(3-chloro-2-pyridinyl)-1H-imidazol-2-yl]-2,2,2-trichloroethanone

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.35 (1H, s), 7.49 (1H, dd, J=8 Hz, 5 Hz),7.95 (1H, dd, J=8 Hz, 2 Hz), 8.51 (1H, dd, J=5 Hz, 2 Hz)

REFERENCE PREPARATION EXAMPLE 151-(3)

To a solution of 0.50 g of1-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-imidazol-2-yl]-2,2,2-trichloroethanoneand 0.37 g of 2-amino-3,5-dibromobenzoic acid in 10 ml of acetonitrilewas added 0.43 ml of triethylamine. The resulting mixture was stirred atroom temperature for 1 day. Thereto 0.12 ml of methanesulfonyl chloridewas added, and the mixture was stirred at room temperature for 3 hours.Water was poured into the reaction mixture, and the mixture wasextracted with ethyl acetate three times. The organic layers werecombined, washed with an aqueous saturated sodium chloride solution,dried over anhydrous magnesium sulfate, and concentrated under reducedpressure. The residue was subjected to silica gel column chromatographyto obtain 0.29 g of2-[4-bromo-1-(3-chloro-2-pyridinyl)-1H-imidazol-2-yl]-6,8-dibromo-4H-3,1-benzoxazine-4-oneof the formula:

2-[4-Bromo-1-(3-chloro-2-pyridinyl)-1H-imidazol-2-yl]-6,8-dibromo-4H-3,1-benzoxazine-4-one

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 7.70 (1H, dd, J=8 Hz, 5 Hz), 8.18 (1H, d,J=3 Hz), 8.18 (1H, s), 8.31 (1H, dd, J=8 Hz, 1Hz), 8.33 (1H, d, J=3 Hz),8.59 (1H, dd, J=5 Hz, 1Hz)

REFERENCE PREPARATION EXAMPLE 152-(1)

A mixture of 0.70 g of1-(3-chloro-2-pyridinyl)-5-thiocyanato-1H-pyrrole-2-carbaldehyde, 0.64 gof sodium sulfide nonahydrate and 10 ml of water was stirred for 1 hourunder heat refluxing. The reaction mixture was allowed to cool to roomtemperature, adjusted to pH 5 by an addition of acetic acid, and thenextracted with ethyl acetate two times. The organic layers werecombined, washed with an aqueous saturated sodium chloride solution,dried over anhydrous magnesium sulfate, and concentrated under reducedpressure. The residue was washed with methyl tert-butyl ether to obtain0.50 g of 1-(3-chloro-2-pyridinyl)-5-mercapto-1H-pyrrole-2-carbaldehydeof the formula:

1-(3-Chloro-2-pyridinyl)-5-mercapto-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.56 (1H, d, J=4 Hz), 7.07 (1H, d, J=4 Hz),7.46 (1H, dd, J=8 Hz, 5 Hz), 7.93 (1H, dd, J=8 Hz, 2 Hz), 8.54 (1H, dd,J=5 Hz, 2 Hz), 9.42 (1H, s)

REFERENCE PREPARATION EXAMPLE 152-(2)

A mixture of 0.50 g of1-(3-chloro-2-pyridinyl)-5-mercapto-1H-pyrrole-2-carbaldehyde, 0.36 g ofmethyl iodide, 0.43 g of potassium carbonate and 50 ml ofN,N-dimethylformamide was stirred at room temperature for 1 day Waterwas poured into the reaction mixture, and the mixture was extracted withethyl acetate three times. The organic layers were combined, washedsuccessively with water and an aqueous saturated sodium chloridesolution, dried over anhydrous magnesium sulfate, and concentrated underreduced pressure. The residue was subjected to silica gel columnchromatography to obtain 0.34 g of1-(3-chloro-2-pyridinyl)-5-methylthio-1H-pyrrole-2-carbaldehyde of theformula:

1-(3-Chloro-2-pyridinyl)-5-methylthio-1H-pyrrole-2-carbaldehyde

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.39 (3H, s), 6.45 (1H, d, J=4 Hz), 7.10(1H, d, J=4 Hz), 7.43 (1H, dd, J=8 Hz, 5 Hz), 7.90 (1H, dd, J=8 Hz, 2Hz), 8.52 (1H, dd, J=5 Hz, 2 Hz), 9.41 (1H, s)

REFERENCE PREPARATION EXAMPLE 152-(3)

To a mixture of 0.38 g of1-(3-chloro-2-pyridinyl)-5-methylthio-1H-pyrrole-2-carbaldehyde, 5 ml ofacetone and 3 ml of water was added 0.38 g of potassium permanganate at40° C. The resulting mixture was stirred at 50° C. for 4 hours. Thereaction mixture was allowed to cool to room temperature, and filtered.The filtrate was washed with chloroform two times, and then adjusted toaround pH 3 by an addition of 2N hydrochloric acid. A deposited crystalwas collected by filtration to obtain 0.38 g of a mixture of1-(3-chloro-2-pyridinyl) 75-methylsulfonyl-1H-pyrrole-2-carboxylic acidand 1-(3-chloro-2-pyridinyl)-5-methylthio-1H-pyrrole-2-carboxylic acid.

A mixture of the resulting mixture and 0.29 ml of thionyl chloride washeated to reflux in 10 ml of acetonitrile for 1 hour. The reactionmixture was allowed to cool to room temperature, and concentrated underreduced pressure. The resulting residue was dissolved in 10 ml ofacetonitrile. Thereto 0.39 g of 2-amino-3,5-dibromobenzoic acid and 0.65ml of triethylamine were added, and the mixture was stirred at roomtemperature for 6 hours. Thereto 0.13 ml of methanesulfonyl chloride wasadded, and the mixture was stirred at room temperature for 1 hour. Waterwas poured into the reaction mixture, and the mixture was extracted withethyl acetate three times. The organic layers were combined, washed withan aqueous saturated sodium chloride solution, dried over anhydrousmagnesium sulfate, and concentrated under reduced pressure. The residuewas subjected to silica gel column chromatography to obtain 0.05 g of6,8-dibromo-2-[1-(3-chloro-2-pyridinyl)-5-methylsulfonyl-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-oneof the formula:

and 0.05 g of6,8-dibromo-2-[1-(3-chloro-2-pyridinyl)-5-methylthio-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-oneof the formula:

6,8-Dibromo-2-[1-(3-chloro-2-pyridinyl)-5-methylsulfonyl-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.23 (3H, s), 7.21 (1H, d, J=4 Hz), 7.41(1H, d, J=4 Hz), 7.50 (1H, dd, J=8 Hz, 4 Hz), 7.95 (1H, d, J=8 Hz), 8.02(1H, d, J=2 Hz), 8.24 (1H, d, J=2 Hz), 8.56 (1H, d, J=4 Hz)

6,8-Dibromo-2-[1-(3-chloro-2-pyridinyl)-5-methylthio-1H-pyrrol-2-yl]-4H-3,1-benzoxazine-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.39 (3H, s), 6.63 (1H, d, J=4 Hz), 7.35(1H, d, J=4 Hz), 7.63 (1H, dd, J=8 Hz, 5 Hz), 8.08 (1H, d, J=2 Hz), 8.22(1H, d, J=2 Hz), 8.25 (1H, dd, J=8 Hz, 2 Hz), 8.58 (1H, dd, J=5 Hz, 2Hz)

REFERENCE PREPARATION EXAMPLE 153-(1)

To a mixture of 20 g of 3-chloro-2-hydrazinopyridine, 56 ml of sodiumethoxide (a 21% solution in ethanol) and 75 ml of ethanol was addeddropwise 27 ml of diethyl maleate. The resulting mixture was heated toreflux for 10 minutes. The reaction mixture was allowed to cool to 65°C., and 15 ml of acetic acid was poured into the mixture. The reactionmixture was allowed to cool to room temperature. After 190 ml of waterwas poured into the reaction mixture, the mixture was adjusted to pH 2by an addition of 6N hydrochloric acid and then extracted with methyltert-butyl ether three times. The organic layers were combined, washedwith an aqueous saturated sodium chloride solution, dried over anhydrousmagnesium sulfate, and concentrated under reduced pressure. Diethylether was added to the resulting residue, and a solid was collected byfiltration to obtain 4.28 g of ethyl2-(3-chloro-2-pyridinyl)-5-oxo-3-pyrazolidinecarboxylate of the formula:

Ethyl 2-(3-chloro-2-pyridinyl)-5-oxo-3-pyrazolidinecarboxylate

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.22 (3H, t, J=7 Hz), 2.36 (1H, d, J=17Hz), 2.92 (1H, dd, J=17 Hz, 10 Hz), 4.20 (2H, q, J=7 Hz), 4.83 (1H, d,J=10 Hz), 7.20 (1H, dd, J=8 Hz, 5 Hz), 7.93 (1H, d, J=8 Hz), 8.27 (1H,d, J=5 Hz), 10.17 (1H, s)

REFERENCE PREPARATION EXAMPLE 153-(2)

To a mixture of 12.0 g of ethyl2-(3-chloro-2-pyridinyl)-5-oxo-3-pyrazolidinecarboxylate, 90 ml ofacetonitrile and 4.8 ml of sulfuric acid was added 14.5 g of potassiumpersulfate. The resulting mixture was heated to reflux for 3.5 hours.The reaction mixture was allowed to cool to room temperature, andfiltered. Water was poured into the filtrate, and the mixture wasextracted with methyl tert-butyl ether three times. The organic layerswere combined, washed with an aqueous saturated sodium chloridesolution, dried over anhydrous magnesium sulfate, and concentrated underreduced pressure. The resulting residue was subjected to silica gelchromatography to obtain 7.23 g of ethyl1-(3-chloro-2-pyridinyl)-3-hydroxy-1H-pyrazole-5-carboxylate of theformula:

Ethyl 1-(3-chloro-2-pyridinyl)-3-hydroxy-1H-pyrazole-5-carboxylate

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 1.06 (3H, t, J=7 Hz), 4.11 (2H, q, J=7Hz), 6.34 (1H, s), 7.59-7.63 (1H, m), 8.17-8.23 (1H, m), 8.50-8.52 (1H,m), 10.65 (1H, s)

REFERENCE PREPARATION EXAMPLE 153-(3)

Trifluoromethyl trifluorovinyl ether was blown into a mixture of 1.0 gof ethyl 1-(3-chloro-2-pyridinyl)-3-hydroxy-1H-pyrazole-5-carboxylate,0.042 g of potassium hydroxide, 10 ml of methanol and 10 ml of dimethylsulfoxide under ice-cooling. The resulting mixture was stirred at roomtemperature for 4 days. Water was poured into the reaction mixture, andthe mixture was extracted with diethyl ether two times. The organiclayers were combined, washed with water and an aqueous saturated sodiumchloride solution, dried over anhydrous magnesium sulfate, andconcentrated under reduced pressure. The resulting residue was subjectedto silica gel chromatography to obtain 1.32 g of methyl1-(3-chloro-2-pyridinyl)-3-[1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy]-1H-pyrazole-5-carboxylateof the formula:

Methyl1-(3-chloro-2-pyridinyl)-3-[1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy]-1H-pyrazole-5-carboxylate

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.80 (3H, s), 6.04 (1H, dt, J=54 Hz, 3 Hz),6.80 (1H, s), 7.45 (1H, dd, J=8 Hz, 5 Hz), 7.92 (1H, dd, J=8 Hz, 2 Hz),8.51 (1H, dd, J=5 Hz, 2 Hz)

REFERENCE PREPARATION EXAMPLE 153-(4)

To a mixture of 1.32 g of methyl1-(3-chloro-2-pyridinyl)-3-[1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy]-1H-pyrazole-5-carboxylateand 15 ml of methanol was added 5 ml of a 2N aqueous sodium hydroxidesolution. The resulting mixture was stirred at room temperature for 3hours. Water was poured into the reaction mixture, and the mixture waswashed with methyl tert-butyl ether. The aqueous layer was adjusted topH 2 by an addition of 6N hydrochloric acid and then extracted withmethyl tert-butyl ether two times. The organic layers were combined,washed with an aqueous saturated sodium chloride solution, dried overanhydrous magnesium sulfate, and concentrated under reduced pressure toobtain 1.18 g of1-(3-chloro-2-pyridinyl)-3-[1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy]-1H-pyrazole-5-carboxylicacid of the formula:

1-(3-Chloro-2-pyridinyl)-3-[1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy]-1H-pyrazole-5-carboxylicAcid

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.04 (1H, dt, J=54 Hz, 3 Hz), 6.84 (1H, s),7.46 (1H, dd, J=8 Hz, 5 Hz), 7.93 (1H, dd, J=8 Hz, 2 Hz), 8.50 (1H, dd,J=5 Hz, 2 Hz)

REFERENCE PREPARATION EXAMPLE 153-(5)

According to the same manner as that of Reference Preparation Example13,1-(3-chloro-2-pyridinyl)-3-[1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy]-1H-pyrazole-5-carboxylicacid was used in place of1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid to obtain6-chloro-2-{1-(3-chloro-2-pyridinyl)-3-[1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy]-1H-pyrazol-5-yl}-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-{1-(3-chloro-2-pyridinyl)-3-[1,1,2-trifluoro-2-(trifluoromethoxy)ethoxy]-1H-pyrazol-5-yl}-8-methyl-4H-3,1-benzoxazin-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.83 (3H, s), 6.06 (1H, dt, J=54 Hz, 3 Hz),7.04 (1H, s), 7.48-7.51 (2H, m), 7.96-8.00 (2H, m), 8.55 (1H, dd, J=5Hz, 2 Hz)

REFERENCE PREPARATION EXAMPLE 154-(1)

To a mixture of 4.0 g of N,N-dimethyl-1H-pyrazole-1-sulfonamide and 50ml of tetrahydrofuran was added dropwise 15.7 ml of a 1.6M solution ofN-butyl lithium in hexane at −78° C. The resulting mixture was stirredat −78° C. for 10 minutes. A mixture of 1.46 g of sulfur and 20 ml oftetrahydrofuran was added to the mixture. The mixture was stirred at−78° C. for 1 hour, and further stirred for 1.5 hours while the reactiontemperature was gradually raised to room temperature. A deposited solidwas collected by filtration, and washed with diethyl ether. The solidwas dissolved in water. The resulting aqueous solution was adjusted toaround pH 3 by an addition of 6N hydrochloric acid, and then extractedwith methyl t-butyl ether three times. The organic layers were combined,washed with an aqueous saturated sodium chloride solution, dried overmagnesium sulfate, and concentrated under reduced pressure to obtain3.92 g of N,N-dimethyl-5-mercapto-1H-pyrazole-1-sulfonamide of theformula:

N,N-Dimethyl-5-mercapto-1H-pyrazole-1-sulfonamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.03 (6H, s), 4.39 (1H, s), 6.27 (1H, d,J=2 Hz), 7.59 (1H, d, J=2 Hz)

REFERENCE PREPARATION EXAMPLE 154-(2)

A mixture of 1.0 g of N,N-dimethyl-5-mercapto-1H-pyrazole-1-sulfonamide,0.30 g of sodium hydride (50% in oil) and 25 ml of tetrahydrofuran wasstirred at room temperature for 0.5 hour, and then cooled to −60° C.Thereto 1.94 g of S-(trifluoromethyl)dibenzothiopheniumtrifluoromethanesulphonate was added. The resulting mixture was stirredat −60° C. for 0.5 hour, and further stirred at room temperature for 2hours. Water was poured into the reaction mixture, and the mixture wasextracted with ethyl acetate three times. The organic layers werecombined, washed with an aqueous saturated sodium chloride solution,dried over magnesium sulfate, and concentrated under reduced pressure.The resulting residue was subjected to silica gel chromatography toobtain 1.30 g ofN,N-dimethyl-5-(triflioromethylthio)-1H-pyrazole-1-sulfonamide of theformula:

N,N-Dimethyl-5-(triflioromethylthio)-1H-pyrazole-1-sulfonamide

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.08 (6H, s), 6.73 (1H, s), 7.73 (1H, s)

REFERENCE PREPARATION EXAMPLE 154-(3)

According to the same manner as that of Reference Preparation Example21, N,N-dimethyl-5-(trifluoromethylthio)-1H-pyrazole-1-sulfonamide wasused in place of 5-bromo-N,N-dimethyl-1H-pyrazole-1-sulfonamide toobtain 3-(trifluoromethylthio)-1H-pyrazole of the formula:

3-(Trifluoromethylthio)-1H-pyrazole

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.70 (1H, d, J=3 Hz), 7.74 (1H, d, J=3 Hz),12.47 (1H, brs)

REFERENCE PREPARATION EXAMPLE 154-(4)

According to the same manner as that of Reference Preparation Example22, 3-(trifluoromethylthio)-1H-pyrazole was used in place of3-bromo-1H-pyrazole to obtain3-chloro-2-[3-(trifluoromethylthio)-1H-pyrazol-1-yl]pyridine of theformula:

3-Chloro-2-[3-(trifluoromethylthio)-1H-pyrazol-1-yl]pyridine

¹H-NMR (CDCl₃, TMS) δ (ppm): 6.78 (1H, d, J=3 Hz), 7.35 (1H, dd, J=8 Hz,5 Hz), 7.94 (1H, dd, J=8 Hz, 2 Hz), 8.17 (1H, d, J=3 Hz), 8.47 (1H, dd,J=5 Hz, 2 Hz)

REFERENCE PREPARATION EXAMPLE 154-(5)

According to the same manner as that of Reference Preparation Example23, 3-chloro-2-[3-(trifluoromethylthio)-1H-pyrazol-1-yl]pyridine wasused in place of 2-(3-bromo-1H-pyrazol-1-yl)-3-chloropyridine to obtain1-(3-chloro-2-pyridinyl)-3-(trifluoromethylthio)-1H-pyrazole-5-carboxylicacid of the formula:

1-(3-Chloro-2-pyridinyl)-3-(trifluoromethylthio)-1H-pyrazole-5-carboxylicAcid

¹H-NMR (CDCl₃, TMS) δ (ppm): 7.35 (1H, s), 7.47 (1H, dd, J=8 Hz, 5 Hz),7.94 (1H, d, J=8 Hz), 8.52 (1H, d, J=5 Hz)

REFERENCE PREPARATION EXAMPLE 154-(6)

According to the same manner as that of Reference Preparation Example13,1-(3-chloro-2-pyridinyl)-3-(trifluoromethylthio)-1H-pyrazole-5-carboxylicacid was used in place of1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxylic acid to obtain6-chloro-2-[1-(3-chloro-2-pyridinyl)-3-(trifluoromethylthio)-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazine-4-oneof the formula:

6-Chloro-2-[1-(3-chloro-2-pyridinyl)-3-(trifluoromethylthio)-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazin-4-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.82 (3H, s), 7.50-7.54 (3H, m), 7.98-8.00(2H, m), 8.57 (1H, dd, J=5 Hz, 2 Hz)

REFERENCE PREPARATION EXAMPLE 155

According to the same manner as that of Reference Preparation Example147,2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6,8-dichloro-4H-3,1-benzoxazin-4-onewas used in place of2-[3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-yl]-6,8-dibromo-4H-3,1-benzoxazin-4-oneto obtain3-bromo-N-[4,6-dichloro-2-(N,N′-dimethylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideof the formula:

3-Bromo-N-[4,6-dichloro-2-(N,N′-dimethylhydrazinocarbonyl)phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.20 (2.4H, d, J=5 Hz), 2.39 (0.6H, d,J=6 Hz), 2.72 (0.6H, s), 3.02 (2.4H, s), 4.59 (0.8H, q, J=5 Hz), 5.68(0.2H, q, J=6 Hz), 7.38 (0.8H, d, J=2 Hz), 7.40 (1.0H, s), 7.53 (0.2H,d, J=2 Hz), 7.60-7.64 (1.0H, m), 7.70 (0.8H, d, J=2 Hz), 7.84 (0.2H, d,J=2 Hz), 8.16-8.19 (1.0H, m), 8.49-8.50 (1.0H, m), 10.34 (0.8H, s),10.65 (0.2H, s)

Then, Formulation Examples will be shown. All parts are by weight.

FORMULATION EXAMPLE 1

Into a mixture of 35 parts of xylene and 35 parts ofN,N-dimethylformamide, 10 parts of any one of the present compounds (1)to (231) is dissolved, and then 14 parts of polyoxyethylene styrylphenylether and 6 parts of calcium dodecylbenzenesulfonate are added. Themixture is stirred thoroughly to obtain a 10% emulsion.

FORMULATION EXAMPLE 2

To a mixture of 4 parts of sodium laurylsulfate, 2 parts of calciumligninsulfonate, 20 parts of synthetic hydrous silicon oxide fine powderand 54 parts of diatomaceous earth, 20 parts of any one of the presentcompounds (1) to (231) is added. The mixture is stirred thoroughly toobtain a 20% wettable agent.

FORMULATION EXAMPLE 3

To 2 parts of anyone of the present compounds (1) to (231), 1 part ofsynthetic hydrous silicon oxide fine powder, 2 parts of calciumligninsulfonate, 30 parts of bentonite and 65 parts of kaolin clay areadded, and then stirred thoroughly. Then, an appropriate amount of wateris added to the mixture. The mixture is further stirred, granulated witha granulator, and forced-air dried to obtain a 2% granule.

FORMULATION EXAMPLE 4

Into an appropriate amount of acetone, 1 part of any one of the presentcompounds (1) to (231) is dissolved, and then 5 parts of synthetichydrous silicon oxide fine powder, 0.3 part of PAP and 93.7 parts offubasami clay are added. The mixture is stirred thoroughly. Then,acetone is removed from the mixture by evaporation to obtain a 1%powder.

FORMULATION EXAMPLE 5

A mixture of 10 parts of any one of the present compounds (1) to (231);35 parts of white carbon containing 50 parts of polyoxyethylene alkylether sulfate ammonium salt; and 55 parts of water is finely ground by awet grinding method to obtain a 10% flowable agent.

FORMULATION EXAMPLE 6

In 5 parts of xylene and 5 parts of trichloroethane, 0.1 part of any oneof the present compounds (1) to (231) is dissolved. The solution ismixed with 89.9 parts of deodorized kerosene to obtain a 0.1% oil.

FORMULATION EXAMPLE 7

In 0.5 ml of acetone, 10 mg of any one of the present compounds (1) to(231) is dissolved. The solution is mixed uniformly with 5 g of a solidfeed powder for an animal (solid feed powder for rearing and breedingCE-2, manufactured by CLEA Japan, Inc.), and then dried by evaporationof acetone to obtain poison bait.

Then, it will be shown by Test Examples that the present compound iseffective in controlling harmful arthropods.

TEST EXAMPLE 1

Preparations of the present compounds (1), (4) to (53), (55) to (74),(76) to (83), (85) to (120), (122) to (156), (158) to (167), (170) to(171), (173), (175) to (176), (178), (181) to (184), (188) to (190),(195) to (197), (200) to (216), (218) to (219), (221) to (223) and (231)obtained in Formulation Example 5 were diluted with water so that theactive ingredient concentration became 500 ppm, to prepare test spraysolutions.

At the same time, cabbage was planted in a polyethylene cup, and grownuntil the third true leaf or the fourth true leaf was developed. Thetest spray solution as described above was sprayed in an amount of 20ml/cup on the cabbage.

After the drug solution sprayed on the cabbage was dried, 10third-instar larvae of diamondback moths were put on the cabbage. After5 days, the number of diamondback moths was counted, and a controllingvalue was calculated by the following equation:

Controlling value(%)={1−(Cb×Tai)/(Cai×Tb)}×100

wherein,

Cb: the number of worms in a non-treated section before treatment

Cai: the number of worms in a non-treated section on observation

Tb: the number of worms in a treated-section before treatment

Tai: the number of worms in a treated-section on observation.

As a result, the test spray solutions of the present compounds (1), (4)to (53), (55) to (74), (76) to (83), (85) to (120), (122) to (156),(158) to (167), (170) to (171), (173), (175) to (176), (178), (181) to(184), (188) to (190), (195) to (197), (200) to (216), (218) to (219),(221) to (223) and (231) each exhibited a controlling value of 80% ormore.

TEST EXAMPLE 2

Preparations of the present compounds (4) to (7), (9) to (12), (17) to(23), (27), (29), (32) to (44), (48) to (51), (56) to (61), (65) to(68), (70) to (72), (74) to (75), (78) to (81), (83) to (85), (87) to(88), (91) to (97), (99) to (102), (104) to (120), (122) to (125), (127)to (135), (137) to (144), (147) to (149), (151) to (161), (164), (166)to (168), (171) to (173), (175) to (184), (186) to (188), (191), (193)to (205), (208) to (209), (213) to (215), (218) to (224), (226) to (230)and (231) obtained in Formulation Example 5 was diluted with water sothat the active ingredient concentration became 500 ppm to prepare testspray solutions.

At the same time, cucumber was planted in a polyethylene cup, and wasgrown until the first true leaf was developed. About 30 cotton aphidswere put on the cucumber. One day after, the test spray solution asdescribed above was sprayed in an amount of 20 ml/cup on the cucumber.Six days after spraying, the number of cotton aphids was counted, and acontrolling value was calculated by the following equation:

Controlling value(%)={1−(Cb×Tai)/(Cai×Tb)}×100

wherein,

Cb: the number of insects in a non-treated section before treatment

Cai: the number of insects in a non-treated section on observation

Tb: the number of insects in a treated-section before treatment

Tai: the number of insects in a treated-section on observation.

As a result, the test spray solutions of the present compounds (4) to(7), (9) to (12), (17) to (23), (27), (29) (32) to (44), (48) to (51),(56) to (61), (65) to (68), (70) to (72), (74) to (75), (78) to (81),(83) to (85), (87) to (88), (91) to (97), (99) to (102), (104) to (120),(122) to (125), (127) to (135), (137) to (144), (147) to (149), (151) to(161), (164), (166) to (168), (171) to (173), (175) to (184), (186) to(188), (191), (193) to (205), (208) to (209), (213) to (215), (218) to(224), (226) to (230) and (231) each exhibited a controlling value of90% or more.

Furthermore, the same way as Test Example 2, test spray solution of thecomparative compound of the formula:

(disclosed in WO2003/015518A page 109 Compound 354) exhibited acontrolling value of less than 30%.

TEST EXAMPLE 3

Preparations of the present compounds (4) to (13), (15) to (23), (25) to(44), (48) to (51), (56) to (58), (61), (65) to (74), (80) to (81), (85)to (97), (100), (102), (104) to (120), (122) to (125), (127) to (137),(139) to (156), (158) to (167), (170) to (171), (173), (175) to (176),(178), (181) to (184), (188) to (190), (195) to (197), (200) to (208),(210) to (216), (218) to (219), (221) to (224) and (231) obtained inFormulation Example 5 was diluted with water so that the activeingredient concentration became 500 ppm to prepare test spray solutions.

At the same time, cabbage was planted in a polyethylene cup, and grownuntil the third true leaf or the fourth true leaf was developed. Thetest spray solution as described above was sprayed in an amount of 20ml/cup on the cabbage. After the drug solution sprayed on the cabbagewas dried, 10 fourth-instar larvae of Spodoptera litura were put on thecabbage. After 4 days, the number of Spodoptera litura surviving on thecabbage leaves was counted, and a controlling value was calculated bythe following equation:

Controlling value(%)={1−(Cb×Tai)/(Cai×Tb)}×100

wherein,

Cb: the number of worms in a non-treated section before treatment

Cai: the number of worms in a non-treated section on observation

Tb: the number of worms in a treated-section before treatment

Tai: the number of worms in a treated-section on observation.

As a result, the test spray solutions of the present compounds (4) to(13), (15) to (23), (25) to (44), (48) to (51), (56) to (58), (61), (65)to (74), (80) to (81), (85) to (97), (100), (102), (104) to (120), (122)to (125), (127) to (137), (139) to (156), (158) to (167), (170) to(171), (173), (175) to (176), (178), (181) to (184), (188) to (190),(195) to (197), (200) to (208), (210) to (216), (218) to (219), (221) to(224) and (231) each exhibited a controlling value of 80% or more.

TEST EXAMPLE 4

Preparations of the present compounds) (4) to (13), (15) to (23), (25)to (45), (47) to (51), (53), (55) to (61), (65) to (72), (74), (78) to(81), (83), (85) to (102), (104) to (105), (107) to (117), (119) to(120), (122) to (125), (127) to (156), (158) to (164), (166) to (167),(171), (173), (175) to (176), (178), (181) to (184), (188) to (190),(195) to (197), (200) to (211), (213) to (216), (218) to (219), (221) to(224) and (231) obtained in Formulation Example 5 was diluted with waterso that the active ingredient concentration became 500 ppm to preparetest spray solutions.

At the same time, 20 ml of the test spray solution as described abovewas sprayed to an apple seedling (28 day-old seeding, tree height: about15 cm) planted in a plastic cup. The apple seedling was air-dried tosuch an extent that the drug solution sprayed on the apple seedling wasdried, about 30 first-instar larvae of Adoxophyes orana fasciata werereleased. Seven days after spraying, the number of worms surviving onthe apple seedling was counted, and a controlling value was calculatedby the following equation:

Controlling value(%)={1−(Cb×Tai)/(Cai×Tb)}×100

wherein,

Cb: the number of worms in a non-treated section before treatment

Cai: the number of worms in a non-treated section on observation

Tb: the number of worms in a treated-section before treatment

Tai: the number of worms in a treated-section on observation.

As a result, the test spray solutions of the present compounds (4) to(13), (15) to (23), (25) to (45), (47) to (51), (53), (55) to (61), (65)to (72), (74), (78) to (81), (83), (85) to (102), (104) to (105), (107)to (117), (119) to (120), (122) to (125), (127) to (156), (158) to(164), (166) to (167), (171), (173), (175) to (176), (178), (181) to(184), (188) to (190), (195) to (197), (200) to (211), (213) to (216),(218) to (219), (221) to (224) and (231) each exhibited a controllingvalue of 90% or more.

TEST EXAMPLE 5

Preparations of the present compounds (4) to (5), (9) to (10), (17),(19) to (22), (27), (29), (32) to (44), (48) to (51), (56) to (61), (66)to (68), (70) to (72), (74) to (75), (79), (81), (85), (88), (91) to(92), (94) to (95), (99), (101) to (102), (104) to (120), (122) to(124), (127) to (129), (131) to (132), (135) to (136), (140), (142) to(145), (147) to (151), (153) to (157), (159), (163) to (164), (167),(171) to (172), (175) to (176), (183), (187), (193) to (194), (196) to(204), (206), (208) to (209), (213) to (221), (226), (227) and (231)obtained in Formulation Example 5 was diluted with water so that theactive ingredient concentration became 500 ppm to prepare test spraysolutions.

At the same time, cucumber was planted in a polyethylene cup, and wasgrown until the first true leaf was developed. The test spray solutionas described above was sprayed in an amount of 20 ml/cup on thecucumber. After the drug solution sprayed on the cucumber was dried, thefirst true leaf was cut and then placed on a filter paper (diameter: 70mm) containing water in a polyethylene cup (diameter: 110 mm). On thecucumber leaf, 20 larvae of Frankliniella occidentalis were released,and the polyethylene cup was capped. Seven days after spraying, thenumber of insects surviving on the cucumber leaf was counted, and acontrolling value was calculated by the following equation:

Controlling value(%)={1−(Cb×Tai)/(Cai×Tb)}×100

wherein,

Cb: the number of insects in a non-treated section before treatment

Cai: the number of insects in a non-treated section on observation

Tb: the number of insects in a treated-section before treatment

Tai: the number of insects in a treated-section on observation.

As a result, the test spray solutions of the present compounds (4) to(5), (9) to (10), (17), (19) to (22), (27), (29), (32) to (44), (48) to(51), (56) to (61), (66) to (68), (70) to (72), (74) to (75), (79),(81), (85), (88), (91) to (92), (94) to (95), (99), (101) to (102),(104) to (120), (122) to (124), (127) to (129), (131) to (132), (135) to(136), (140), (142) to (145), (147) to (151), (153) to (157), (159),(163) to (164), (167), (171) to (172), (175) to (176), (183), (187),(193) to (194), (196) to (204), (206), (208) to (209), (213) to (221),(226), (227) and (231) each exhibited a controlling value of 90% ormore.

TEST EXAMPLE 6

Preparations of the present compounds (5), (32), (34), (43) to (44),(49) to (50), (56), (59), (93), (95) to (96), (107), (111) to (112),(114), (119), (127), (129), (132) to (133), (144), (147) to (148),(153), (158), (167) to (168), (171) to (172), (177) to (178), (182) to(184), (186) to (187), (193) to (194), (197) to (199), (201), (204),(209), (213), (215), (219) to (220), (221), (223), (226) and (231)obtained in Formulation Example 5 was diluted with water so that theactive ingredient concentration became 500 ppm to prepare test spraysolutions.

At the same time, cabbage was planted in a polyethylene cup, and grownuntil the first true leaf was developed. All leaves excluding the firsttrue leaf were cut off. On the first true leaf, imagoes of silver leafwhitefly were released and allowed to lay eggs for about 24 hours. Thecabbage was retained in a greenhouse for 8 days. When larvae hatchedfrom the laid eggs, the test spray solution as described above wassprayed in an amount of 20 ml/cup to the cabbage. Seven days afterspraying, the number of larvae surviving on the cabbage was counted, anda controlling value was calculated by the following equation:

Controlling value(%)={1−(Cb×Tai)/(Cai×Tb)}×100

wherein,

Cb: the number of worms in a non-treated section before treatment

Cai: the number of worms in a non-treated section on observation

Tb: the number of worms in a treated-section before treatment

Tai: the number of worms in a treated-section on observation.

As a result, the test spray solutions of the present compounds (5),(32), (34), (43) to (44), (49) to (50), (56) (59), (93), (95) to (96),(107), (111) to (112), (114), (119), (127), (129), (132) to (133),(144), (147) to (148), (153), (158), (167) to (168), (171) to (172),(177) to (178), (182) to (184), (186) to (187), (193) to (194), (197) to(199), (201), (204), (209), (213), (215), (219) to (220), (221), (223),(226) and (231) each exhibited a controlling value of 90% or more.

INDUSTRIAL APPLICABILITY

According to the present invention, since the hydrazide compound of thepresent invention has excellent efficacy of controlling pests, it isuseful as an active ingredient of a pesticide.

1. A compound represented by the formula (2-i):

wherein, R² and R³ independently represent a hydrogen atom, a C1-C6alkyl group optionally substituted with at least one halogen atom, aC1-C6 acyl group, a C2-C6 alkoxycarbonyl group, a C3-C7N,N-dialkylcarbamoyl group, or a phenyl group optionally substitutedwith 1 to 5 independent substituents selected from the group consistingof (1) a halogen atom, (2) a cyano group, (3) a nitro group and (4) aC1-C6 alkyl group optionally substituted with at least one halogen atom,R⁴ represents a halogen atom, a cyano group, a nitro group, a C1-C6alkyl group optionally substituted with at least one halogen atom, aC1-C6 alkoxy group optionally substituted with at least one halogenatom, a phenyl group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom, or two R⁴ groups which arebound to the adjacent carbon atoms are bound at their terminal ends toeach other to form a group T1 or T2 T1: —CR⁴¹═CR⁴²—CR⁴³═CR⁴⁴— T2:—(CR⁴⁵R⁴⁶)_(h)— (wherein R⁴¹, R⁴², R⁴³ and R⁴⁴ independently represent ahydrogen atom, a halogen atom, a cyano group, a nitro group, a C1-C6alkyl group optionally substituted with at least one halogen atom, aC1-C6 alkoxy group optionally substituted with at least one halogenatom, a C1-C6 alkylthio group optionally substituted with at least onehalogen atom, a C1-C6 alkylsulfinyl group optionally substituted with atleast one halogen atom, or a C1-C6 alkylsulfonyl group optionallysubstituted with at least one halogen atom, R⁴⁵ and R⁴⁶ independentlyrepresent a hydrogen atom, or a C1-C6 alkyl group optionally substitutedwith at least one halogen atom, and h represents an integer of 3 or 4),n represents an integer of 0 to 4 (provided that, when n is an integerof 2 or more, R⁴'s may be the same or different), J represents a grouprepresented by J1 or J2:

(wherein X^(a), Y^(a), Z^(a), X^(b), Y^(b) and Z^(b) independentlyrepresent CH or a nitrogen atom, R^(13a) and R^(13b) represent a C1-C6alkyl group optionally substituted with at least one halogen atom; aC2-C6 cyanoalkyl group; a C2-C6 alkoxyalkyl group optionally substitutedwith at least one halogen atom; a C2-C6 alkenyl group optionallysubstituted with at least one halogen atom; a C2-C6 alkynyl groupoptionally substituted with at least one halogen atom; a C3-C6cycloalkyl group optionally substituted with one or more independentsubstituents selected from the group consisting of (1) a halogen atomand (2) a C1-C6 alkyl group; a phenyl group optionally substituted with1 to 5 independent substituents selected from the group consisting of(1) a halogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6alkyl group optionally substituted with at least one halogen atom, (5) aC1-C6 alkoxy group optionally substituted with at least one halogenatom, (6) a C1-C6 alkylthio group optionally substituted with at leastone halogen atom, (7) a C1-C6 alkylsulfinyl group optionally substitutedwith at least one halogen atom and (8) a C1-C6 alkylsulfonyl groupoptionally substituted with at least one halogen atom; a 5- to6-membered heteroaryl group optionally substituted with one or moreindependent substituents selected from the group consisting of (1) ahalogen atom, (2) a cyano group, (3) a nitro group, (4) a C1-C6 alkylgroup optionally substituted with at least one halogen atom and (5) aC1-C6 alkoxy group optionally substituted with at least one halogenatom; a C7-C9 phenylalkyl group in whose benzene ring moiety may besubstituted with one or more independent substituents selected from thegroup consisting of (1) a halogen atom, (2) a cyano group, (3) a nitrogroup, (4) a C1-C6 alkyl group optionally substituted with at least onehalogen atom and (5) a C1-C6 alkoxy group optionally substituted with atleast one halogen atom; and a C7-C9 pyridinylalkyl group whose pyridinering moiety may be substituted with one or more independent substituentsselected from the group consisting of (1) a halogen atom, (2) a cyanogroup, (3) a nitro group, (4) a C1-C6 alkyl group optionally substitutedwith at least one halogen atom and (5) a C1-C6 alkoxy group optionallysubstituted with at least one halogen atom, R^(14a) and R^(14b)represent a halogen atom; a cyano group; a nitro group; an isocyanatogroup; a C1-C6 alkyl group optionally substituted with at least onehalogen atom; a C1-C6 alkoxy group optionally substituted with at leastone halogen atom; a C2-C6 cyanoalkyloxy group; a C3-C6 alkoxyalkyloxygroup optionally substituted with at least one halogen atom; a C3-C6alkenyloxy group optionally substituted with at least one halogen atom;a C3-C6 alkynyloxy group optionally substituted with at least onehalogen atom; a C1-C6 alkylthio group optionally substituted with atleast one halogen atom; a C1-C6 alkylsulfinyl group optionallysubstituted with at least one halogen atom; a C1-C6 alkylsulfonyl groupoptionally substituted with at least one halogen atom; a phenyl groupoptionally substituted with 1 to 5 independent substituents selectedfrom the group consisting of (1) a halogen atom, (2) a cyano group, (3)a nitro group, (4) a C1-C6 alkyl group optionally substituted with atleast one halogen atom and (5) a C1-C6 alkoxy group optionallysubstituted with at least one halogen atom; a 5- to 6-memberedheteroaryl group optionally substituted with one or more independentsubstituents selected from the group consisting of (1) a halogen atom,(2) a cyano group, (3) a nitro group, (4) a C1-C6 alkyl group optionallysubstituted with at least one halogen atom and (5) a C1-C6 alkoxy groupoptionally substituted with at least one halogen atom; or a phenoxygroup optionally substituted with 1 to 5 independent substituentsselected from the group consisting of (1) a halogen atom, (2) a cyanogroup, (3) a nitro group, (4) a C1-C6 alkyl group optionally substitutedwith at least one halogen atom and (5) a C1-C6 alkoxy group optionallysubstituted with at least one halogen atom, p represents an integer of 0to 3, and q represents an integer of 0 to 3 (provided that, when p is aninteger of 2 or 3, two or more R^(14a)'s may be the same or differentand, when q is an integer of 2 or 3, two or more R^(14b)'s may be thesame or different).